Coloring composition, method for manufacturing a color filter using the same, color filter and solid-state imaging device

ABSTRACT

There is provided a coloring composition including: a colorant; and a resin, wherein a content of the colorant is 50% by mass or more based on total solids of the coloring composition, and a solid acid number of a resin having a highest solid acid number among all kinds of resins contained in the coloring composition, is 80 mg KOH/g or less.

CROSS-REFERENCE TO RELATED APPLICATION(S)

This is a continuation of International Application No.PCT/JP2012/072832 filed on Aug. 31, 2012, and claims priority fromJapanese Patent Application No. 2011-190186 filed on Aug. 31, 2011, theentire disclosures of which are incorporated herein by reference.

TECHNICAL FIELD

The present invention relates to a method for manufacturing a colorfilter, a color filter and a solid-state imaging device.

For example, in a solid-state imaging device, a color filter isistalled, in which colored pixels of a plurality of colors such as redpixels, green pixels and blue pixels are two-dimensionally arranged on asupport such as a semiconductor substrate. Recently, in the solid-stateimaging device, the increase in the number of pixels has beensignificant. The reduction in the pixel size is significant as comparedwith the same inch-sized solid-state imaging device in the related art.Further, as the pixel size reduces, performance requirements for colorseparation have been rigorous, and in order to maintain devicecharacteristics such as color shading characteristics and prevention ofcolor mixing, the performance of a color filter requires thinning,rectangularity and removal of an overlapped region in which colors areoverlapped between each colored pixel and the like.

BACKGROUND ART

As a method for manufacturing the color filter, a photolithography hasbeen widely used for a long time. The photolithography is a methodincluding: coating and drying a coloring photosensitive composition on asupport to form a colored layer, then exposing and developing thecolored layer to form a colored pixel of a first tint (for example,green), and forming a colored pixel of the remaining colors in the samemanner.

However, as the pixels of a solid-state imaging device are micronized,it has become difficult to achieve both spectral characteristics andpattern formability of a color filter for the demand for micronizationand thinning of the color filter in the pattern formation by a so-calledphotolithography. Specifically, in a color filter for a solid-stateimaging device, the thickness thereof tends to become, for example, 1 μmor less for the thinning of a colored pattern and to become 2 μm or less(for example, 0.5 μm to 2.0 μm) for the pixel pattern size, therebyachieving a microsize.

In particular, as the thinning of a film progresses, the relative amountof colorants such as pigments in a film increases, while the amount ofcomponents other than the colorants, which contribute to thephotolithographic properties, in a film relatively decreases, and thepattern formability due to the decrease has effects of improving theshape of a pattern observed on the top surface thereof even when acorrection such as OPC is performed for the requirement of forming apattern below 2.0 μm, but there is a problem such as insufficientrectangularity that the pattern edge of the pattern shape is round whenobserved the cross-section. It is known that in a color filter (a colorfilter manufactured by photolithography using a coloring radiationsensitive composition in which a pigment is dispersed in variouscompositions) using a pigment dispersion liquid, the rounding of thepattern edge become significant by influence of light scattering by thepigment when exposuring.

In particular, recently, due to the demand for the higher definition ofthe color filter for a solid-state imaging device, the formability of apattern of, for example, 1.4 μm becomes problematic, and thus, theresolution may almost reach a limit in the photolithography in therelated art.

For a method for manufacturing a color filter using thephotolithography, a processing method using dry etching has beensuggested as a method effective to realize micronization and thinning ofa pattern. The dry etching has been adopted in the related art as amethod for forming a pattern (each colored pixel) in a rectangular form,and a method for forming a pattern which combines the photolithographyand the dry etching have been suggested (see, for example, PatentDocuments Japanese Patent Application Laid-Open No. 2006-222290 andJapanese Patent Application Laid-Open No. 2007-48774).

However, for the purpose of further enhancing the performance of thesolid-state imaging device, it has been still required to suppress acrosstalk (color mixing of light). As a method to solve this, atechnique for further thinning the thickness of colored pixels iscontemplated. However, in this case, a simple thinning process causes aproblem that color formation is insufficient. Therefore, as a techniqueto solve this problem, it is contemplated to increase the concentrationof a colorant in colored pixels. However, on the other hand, it isunderstood that a problem arises in that dispersion stability is damagedin the liquid of the coloring composition for making colored pixels.

The present invention has been made in consideration of theabove-described problems. Therefore, an object of the present inventionis to provide a coloring composition having excellent dispersionstability of a colorant in a liquid while containing a highconcentration of the colorant in order to further thin colored pixels.

Further, another object of the present invention is to provide acoloring composition capable of reducing the occurrence of overlapregion overlapped with colors in other colored layers by forming coloredpixels having excellent solvent resistance and alkaline developingsolution resistance, and having small change in color in variousprocesses of manufacturing a color filter, thereby making it possible toprepare a color filter having high performance.

Further, still another object of the present invention is to provide amethod for preparing a color filter using the coloring composition, acolor filter and a solid-state imaging device.

SUMMARY OF INVENTION

The detailed means to solve the above problems is described as follows.

(1) A coloring composition including: a colorant; and a resin, wherein acontent of the colorant is 50% by mass or more based on total solids ofthe coloring composition, and a solid acid number of a resin having ahighest solid acid number among all kinds of resins contained in thecoloring composition, is 80 mg KOH/g or less.(2) A method for manufacturing a color filter including: (a) forming afirst colored layer with a first coloring composition; and (b)patterning the first coloring composition by dry etching to form a groupof through-holes in the first colored layer, wherein the first coloringcomposition is the coloring composition according to (1).(3) The method according to (2), wherein the group of through-holesincludes a first group of through-holes and a second group ofthrough-holes, the method further including: (c) stacking a secondcolored radiation sensitive layer with a second coloring radiationsensitive composition on the first colored layer such that the secondcoloring radiation sensitive composition is embedded inside each of thethrough-holes in the first group of the through-holes and the secondgroup of the through-holes so as to form a plurality of second coloredpixels; (d) removing the second colored radiation sensitive layer and aplurality of the second colored pixels formed inside each of thethrough-holes in the second group of the through-holes by exposing anddeveloping a position in the second colored radiation sensitive layer,which corresponds to the first group of the through-holes formed in thefirst colored layer; (e) stacking a third colored radiation sensitivelayer with a third coloring radiation sensitive composition on the firstcolored layer such that the third coloring radiation sensitivecomposition is embedded inside each of the through-holes in the secondgroup of the through-holes so as to form a plurality of third coloredpixels; and (f) removing the third colored radiation sensitive layer byexposing and developing a position in the third colored radiationsensitive layer, which corresponds to the second group of thethrough-holes formed in the first colored layer.(4) The method according to (2) or (3), wherein the second coloringradiation sensitive composition contains a colorant in amount of 30% bymass or more based on total solids of the second coloring radiationsensitive composition, and the third coloring radiation sensitivecomposition contains a colorant in amount of 30% by mass or more basedon total solids of the third coloring radiation sensitive composition,and the second coloring composition contains a colorant in amount of 30%by mass or more based on total solids of the third coloring radiationsensitive composition.(5) The method according to any one of (2) to (4), wherein the firstcolored layer is a green transmitting layer.(6) The method according to (5), wherein one of the second pixels andthe third pixels is a red transmitting part, and the other is bluetransmitting part.(7) A color filter obtained by the method for preparing a color filteraccording to any one of (2) to (6).(8) A solid-state imaging device including the color filter of (7).

According to the present invention, there is provided a coloringcomposition having excellent dispersion stability of a colorant in aliquid while containing a high concentration of the colorant in order tofurther thin colored pixels.

Further, there is provided a coloring composition capable of reducingthe occurrence of overlap region overlapped with colors in other coloredlayers by forming colored pixels having excellent solvent resistance andalkaline developing solution resistance, and having small change incolor in various processes of manufacturing a color filter, therebymaking it possible to prepare a color filter having high performance.

Further, according to the present invention, there are provided a methodfor preparing a color filter using the coloring composition, a colorfilter and a solid-state imaging device.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic cross-sectional view illustrating an exemplaryconfiguration of a color filter and a solid-state imaging device.

FIG. 2 is a schematic cross-sectional view of a first colored layer.

FIG. 3 is a schematic cross-sectional view illustrating a state where aphotoresist layer is formed on the first layer.

FIG. 4 is a schematic cross-sectional view illustrating a state where aresist pattern is formed on the first layer.

FIG. 5 is a schematic cross-sectional view illustrating a state where afirst colored pattern is formed by providing a group of through-holes inthe first layer by etching.

FIG. 6 is a schematic cross-sectional view illustrating a state wherethe resist pattern is removed.

FIG. 7 is a schematic cross-sectional view illustrating a state where asecond colored pattern and a second colored radiation sensitive layerare formed.

FIG. 8 is a schematic cross-sectional view illustrating a state wherethe second colored radiation sensitive layer and a part of secondcolored pixels constituting the second colored pattern of FIG. 7 areremoved.

FIG. 9 is a schematic cross-sectional view illustrating a state where athird colored pattern and a third colored radiation sensitive layer areformed.

FIG. 10 is a schematic cross-sectional view illustrating a state wherethe third colored radiation sensitive layer of FIG. 9 is removed.

DESCRIPTION OF EMBODIMENTS

Hereinafter, the composition of the present invention will be describedin detail.

In representation of a group (atomic group) in the presentspecification, the representation which does not describe “substituted”and “unsubstituted” also includes a representation having substituentsalong with a representation having no substituent. For example, “analkyl group” includes an alkyl group having no substituent (anunsubstituted alkyl group) and an alkyl group having substituents (asubstituted alkyl group).

The explanation of constitutional requirements described hereinafter maybe made based on the representative embodiment of the present invention,but the present invention is not limited to such an embodiment.Meanwhile, in the present specification, a numerical range representedby using “to” denotes a range including numerical values describedbefore and after “to” as a lower limit and an upper limit.

Meanwhile, in the present specification, “(meth)acrylate” representsacrylate and methacrylate, “(meth)acryl” represents acryl and methacryl,and “(meth)acryloyl” represents acryloyl and methacryloyl. Further, inthe present specification, “monomeric body” and “monomer” are synonymouswith each other. In the present invention, monomer is differentiatedfrom oligomer and polymer, and refers to a compound having a massaverage molecular weight of less than 2,000. In the presentspecification, the polymerizable compound refers to a compound having apolymerizable group, and may be a monomer or a polymer. Thepolymerizable group refers to a group which is involved in apolymerization reaction.

<Coloring Composition>

The coloring composition of the present invention contains a colorantand a resin. In the coloring composition of the present invention, acontent of the colorant is 50% by mass or more based on the total solidsof the coloring composition, and the corresponding solid acid number ofa resin having the highest solid acid number is 80 mgKOH/g or less amongthe entire resins contained in the coloring composition.

Hereinafter, each component constituting the coloring composition of thepresent invention will be described.

[1] Colorant

The coloring composition of the present invention contains at least oneof colorants. The colorant is not particularly limited, and a mixture ofone or two or more of various dyes or pigments known in the related artmay be used.

As the pigment, various inorganic pigments or organic pigments known inthe art may be used. Further, when it is considered that it is preferredthat any of inorganic pigments or organic pigments has a hightransmittance, it is preferred to use a pigment having an averageparticle diameter as small as possible, and when the handling ability isconsidered, the average particle diameter of the pigment is preferably0.01 μm to 0.1 μm, and more preferably 0.01 μm to 0.05 μm.

Pigments which may be preferably used in the present invention are asfollows. However, the present invention is not limited thereto.

C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17,18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53,55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100,101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120,123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152,153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172,173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194,199, 213, 214 and the like,

C.I. Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49,51, 52, 55, 59, 60, 61, 62, 64, 71, 73 and the like,

C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41,48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1,63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123,144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177,178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210,216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272 and 279

C.I. Pigment Green 7, 10, 36, 37 and 58

C.I. Pigment Violet 1, 19, 23, 27, 32, 37 and 42

C.I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60,64, 66, 79 and 80

C.I. Pigment Black 1

These organic pigments may be used either alone or in combination ofvarious pigments in order to enhance the color purity.

In the present invention, when the colorant is a dye, a coloringcomposition which is uniformly dissolved in the composition may beobtained.

The dye is not particularly limited, and a dye for a color filter knownin the related art may be used.

As the chemical structure, dyes such as pyrazole azo-based, anilinoazo-based, triphenylmethane-based, anthraquinone-based,anthrapyridone-based, benzilidene-based, oxonol-based, pyrazolotriazoleazo-based, pyridone azo-based, cyanine-based, phenothiazine-based,pyrrolo pyrazole azomethine-based, xanthene-based, phthalocyanine-based,benzopyran-based, indigo-based and pyromethene-based dyes may be used.Further, a multimer of these dyes may be used.

In addition, as the colorant, an acidic dye and/or a derivative thereofmay be suitably used.

Besides, it is possible to usefully use a direct dye, a basic dye, amordant dye, an acidic mordant dye, an azoic dye, a disperse dye, anoil-soluble dye, a food dye, and/or a derivative thereof and the like.

Hereinafter, specific examples of the acidic dye will be enumerated, butare not limited thereto. Examples thereof include acid alizarin violetN; acid black 1, 2, 24 and 48; acid blue 1, 7, 9, 15, 18, 23, 25, 27,29, 40 to 45, 62, 70, 74, 80, 83, 86, 87, 90, 92, 103, 112, 113, 120,129, 138, 147, 158, 171, 182, 192, 243 and 324:1; acid chrome violet K;acid Fuchsin; acid green 1, 3, 5, 9, 16, 25, 27 and 50; acid orange 6,7, 8, 10, 12, 50, 51, 52, 56, 63, 74 and 95; acid red 1, 4, 8, 14, 17,18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87,88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150,151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266 and274; acid violet 6B, 7, 9, 17 and 19; acid yellow 1, 3, 7, 9, 11, 17,23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116,184 and 243; Food Yellow 3; and derivatives of these dyes.

Besides the above, acidic dyes such as azo-based, xanthene-based andphthalocyanine-based acidic dyes, and C.I. Solvent Blues 44 and 38; C.I.Solvent Orange 45; Rhodamine B and Rhodamine 110 dyes, and derivativesof these dyes are also preferably used.

Among them, the colorant is preferably selected fromtriarylmethane-based, anthraquinone-based, azomethine-based,benzylidene-based, oxonol-based, cyanine-based, phenothiazine-based,pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based,benzopyran-based, indigo-based, pyrazole azo-based, anilino azo-based,pyrazolotriazole azo-based, pyridone azo-based, anthrapyridone-based andpyromethene-based colorants.

Further, pigments and dyes may be used in combination.

The colorant in the present invention is preferably a dye or a pigment.In particular, a pigment having an average particle diameter (r)satisfying 20 nm≦r≦300 nm, preferably 25 nm≦r≦250 nm, and particularlypreferably 30 nm≦r≦200 nm is preferred. A pixel having a high contrastratio and a high light transmittance may be obtained by using a pigmenthaving the average particle diameter. As used herein, the term “averageparticle diameter” means an average particle diameter of secondaryparticles in which primary particles (single crystallites) of a pigmentare aggregated. The average primary particle diameter may be obtained bymeasuring 100 particle sizes in portions where particles are notaggregated by observation through SEM or TEM and calculating the averagevalue thereof.

In addition, the particle diameter distribution of secondary particlesof a pigment which may be used in the present invention (hereinafter,simply referred to as “particle diameter distribution”) is suitable whensecondary particles with diameter range within (average particlediameter ±100) nm are present in an amount of 70% by mass, andpreferably 80% by mass based on the entire secondary particles.

A pigment having the above-described average particle diameter andparticle diameter distribution may be prepared by using a commerciallyavailable pigment together with another pigment (the average particlediameter thereof usually exceeds 300 nm) used in some cases to prepare apigment mixture solution in which a dispersion agent and a solvent arepreferably mixed, and mixing and dispersing the pigment mixture solutionwhile pulverizing the pigment by using a pulverizer such as, forexample, bead mill and roll mill. The pigment thus obtained usuallytakes a form of pigment dispersion liquid.

—Micronization of Pigment—

In the present invention, a fine and particle-size-regulated organicpigment may be used if necessary. Micronization of the pigment isachieved through a process which includes preparing a highly viscousliquid composition together with the pigment, a water-soluble organicsolvent and water-soluble inorganic salts and adding stress and grindingthe pigment by using a wet pulverizing apparatus and the like.

Examples of the water-soluble organic solvent used in the micronizationprocess of the pigment include methanol, ethanol, isopropanol,n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol,diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,diethylene glycol monobutyl ether, propylene glycol, propylene glycolmonomethyl ether acetate and the like.

Further, other solvents which have a low water-solubility or nowater-solubility, for example, benzene, toluene, xylene, ethylbenzene,chlorobenzene, nitrobenzene, aniline, pyridine, quinoline,tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, butylacetate, hexane, heptane, octane, nonane, decane, undecane, dodecane,cyclohexane, methylcyclohexane, halogenated hydrocarbon, acetone, methylethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide,dimethylsulfoxide, N-methylpyrrolidone, or the like may be used as longas the amount thereof is so small that the solvent is adsorbed on thepigment and do not flow into waste water.

The solvent used in the micronization process of the pigment may be usedeither alone or in combination of two or more if necessary.

In the present invention, examples of the water-soluble inorganic saltused in the micronization process of the pigment include sodiumchloride, potassium chloride, calcium chloride, barium chloride, sodiumsulfate and the like.

The amount of the water-soluble inorganic salt used in the micronizationprocess is 1 time by mass to 50 times by mass the amount of the pigment,and more preferably 1 time by mass to 10 times by mass the amount of thepigment, from the viewpoint of productivity, although a greater amountprovides a higher grinding effect. Further, it is preferred thatinorganic salts with a moisture content of 1% or less are used.

The amount of the water-soluble organic solvent used in themicronization process is 50 parts by mass to 300 parts by mass, andpreferably 100 parts by mass to 200 parts by mass, based on 100 parts bymass of the pigment.

The operation conditions of the wet pulverizing apparatus in themicronization process of the pigment are not particularly limited, butin order to effectively perform milling by a pulverizing media, in theoperation conditions when a kneader is used as an apparatus, the numberof rotations of a blade in the apparatus is preferably from 10 rpm to200 rpm, and the rotation ratio between two axes is preferablyrelatively higher because a higher grinding effect is obtained. Theoperation time including a dry pulverizing time is preferably 1 hour to8 hours, and the internal temperature of the apparatus is preferably 50°C. to 150° C. In addition, the water-soluble inorganic salt as apulverizing media preferably has a pulverized particle size of 5 μm to50 μm, a sharp particle diameter distribution, and a spherical shape.

—Combination of Pigments—(Color Matching)

These organic pigments may be used either alone or in combinationthereof in order to enhance the color purity. Specific examples of thecombination will be shown in the following. For example, as a redpigment, anthraquinone-based pigments, perylene-based pigments anddiketopyrrolopyrrole-based pigments may be used, either alone or inmixture of at least one thereof, with disazo-based yellow pigments,isoindoline-based yellow pigments and quinophthalone-based yellowpigments or perylene-based red pigments, anthraquinone-based redpigments and diketopyrrolopyrrole-based red pigments, or the like.Examples of the anthraquinone-based pigments include C.I. Pigment Red177, examples of the perylene-based pigments include C.I. Pigment Red155 and C.I. Pigment Red 224, and examples of thediketopyrrolopyrrole-based pigments include C.I. Pigment Red 254, andfrom the viewpoint of color reproducibility, a mixture with C.I. PigmentYellow 83, C.I. Pigment Yellow 139 or C.I. Pigment Red 177 is preferred.Further, the mass ratio of the red pigment to other pigments ispreferably 100:5 to 100:80. Within this range, light transmittance in arange from 400 nm to 500 nm is suppressed to improve the color purityand a sufficient color developing power is achieved. In particular, themass ratio is optimally 100:10 to 100:65. Meanwhile, in the case of acombination of red pigments, the mass ratio may be adjusted inaccordance with the chromaticity.

In addition, as a green pigment, halogenated phthalocyanine-basedpigments may be used either alone or in mixture of the halogenatedphthalocyanine-based pigment with disazo-based yellow pigments,quinophthalone-based yellow pigments, azomethine-based yellow pigementsor isoindoline-based yellow pigments. For example, as an example thereofa mixture with C.I. Pigment Green 7, 36, 37 and 58 and C.I. PigmentYellow 83, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I.Pigment Yellow 150, C.I. Pigment Yellow 180 or C.I. Pigment Yellow 185is preferred. The mass ratio of the green pigment to the yellow pigmentis preferably 100:5 to 100:200. In the mass ratio within theabove-described range, the light transmittance in a range of 400 nm to450 nm may be suppressed to improve the color purity, and a color in thevicinity of an NTSC target color which is a designed value as it is maybe obtained without the main wavelength thereof being in the vicinity ofthe long wavelength. The mass ratio is particularly preferably 100:20 to100:150.

As a blue pigment, phthalocyanine-based pigments may be used eitheralone or in mixture of the phthalocyanine-based pigment withdioxazine-based violet pigments. Particularly suitable examples thereofinclude mixtures with C.I. Pigment Blue 15:6 and C.I. Pigment Violet 23.

The mass ratio of the blue pigment to the violet pigment is preferably100:0 to 100:100, and more preferably 100:70 or less.

In the coloring composition of the present invention, the content of acolorant is 50% by mass or more, preferably 55% by mass or more, andmore preferabley 60% by mass or more based on the total solids of thecoloring composition. In such a content, for example, in order topromote suppressing a crosstalk (color mixing of light), even if thethickness of colored pixels obtained from the coloring composition ismade very thin (for example, 0.7 μm or less), it is possible to obtain asufficient color formation. In contrast, if the content of the colorantis less than 50% by mass based on the total solids of the coloringcomposition, it is difficult to obtain a sufficient color formation whenthe thickness of the colored pixels is made very thin as describedabove.

In addition, although there is no particular limitation on the upperlimit of the colorant based on total solids of the coloring composition,the content may be, for example, 99.5% by mass or less.

[2] Resin

The coloring composition of the present invention contains a resin. Theresin may be exemplified by a resin functioning as a dispersion resinwhich disperses the above-described colorant, or a resin functioning asa binder resin. In addition, the resin may function as a dispersionresin as well as a binder resin.

As described above, the corresponding solid acid number of the resinhaving the highest solid acid number (hereinafter, the acid number willbe referred to as “maximum solid acid number of resin” as well) amongall kinds of resins contained in the coloring composition, is 80 mgKOH/g or less. In such an embodiment, the dispersion stability of thecolorant in the liquid of the composition may become excellent. It isconsidered that this is because the formation of hydrogen bondingbetween resins is suppressed and the increase in viscosity is, in turn,suppressed by using a resin having few acid groups. Further, when onlyone kind of resin is contained in the coloring composition, the maximumsolid acid number of resins is the acid number of the one kind of resin.

In addition, since the maximum solid acid number of resins is 80 mgKOH/g or less, even in the case where the colored layer formed by thecoloring composition of the present invention comes into contact withorganic solvents in other coloring compositions or an alkalinedeveloping solution during manufacturing a color filter, the coloredlayer has high durability with respect to these liquids, and it ispossible to suppress the occurrence of color loss in the colored layeror the occurrence of overlap region in which a plurality of colors areoverlapped with each other, thereby improving in the performance of thecolor filter finally obtained.

Particularly, in the case where a somewhat high polar solvent is used asa solvent for other coloring compositions, since the maximum solid acidnumber of resins is 80 mg KOH/g or less according to the colored layerformed by the coloring composition of the present invention, it isconsidered that the affinity with such a solvent is lowered, and solventresistance is enhanced. In addition, since the maximum solid acid numberof resins is 80 mg KOH/g or less, it is considered that the coloredlayer formed by the coloring composition of the present invention hasdecreased solubility in a developing solution (especially, alkinedeveloping solution), and thus, solvent resistance is enhanced.

The highest solid acid number of the resin is preferably 70 mg KOH/g orless, and more preferably 60 mg KOH/g or less.

When the highest solid acid number of the resin is 0 mg KOH/g, the valueis within the range of the present invention and is a preferred form,but when the highest solid acid number of the resin exceeds 0 mg KOH/g,the highest solid acid number of the resin is, for example, 1 mg KOH/gor more.

The solid acid number of the resin may be adjusted by adjusting theamount of the acid group in the resin.

More specifically, the dispersion resin in the present invention may ormay not have a structural unit (repeating unit) having an acid group,but when the dispersion resin has a structural unit having an acidgroup, the content of the structural unit having an acid group ispreferably 1% by mass to 40% by mass, more preferably 1% by mass to 30%by mass, and still more preferably 1% by mass to 20% by mass, based onthe total mass of the dispersion resin.

The content of the structural unit having an acid group is within theabove-described range, and thus, the acid number of the dispersion resinmay be suitably adjusted to 80 mg KOH/g or less.

Examples of the acid group include a carboxylic acid group, a sulfonicacid group, a phosphoric acid group, a phenolic hydroxyl group and thelike. The acid groups may be used either alone or in combination of twoor more kinds thereof.

In the present invention, the acid number of the dispersion resin may becalculated, for example, from the average content of acid groups in thedispersion resin. In addition, a resin having a desired acid number maybe obtained by changing the content of a monomer unit containing an acidgroup, which constitutes the dispersion resin.

As the dispersion resin, many kinds of compounds may be used, but amongthem, the dispersion resin in the present invention is preferably agraft polymer. The graft polymer preferably has a graft chain having thenumber of atoms except hydrogen atoms in a range of 40 to 10,000, andthe graft chain in this case indicates a portion from the source of themain chain of a copolymer (an atom which binds with the main chain in agroup branched from the main chain) to the terminal of the groupbranched from the main chain. In the coloring composition, thedispersion resin is a dispersion resin which imparts dispersibility to acolorant (particularly, a pigment), and the dispersion resin hasaffinity for the solvent by the graft chain, and thus the dispersibilityand dispersion stability after the passage of time of the colorant areexcellent. Further, when the dispersion resin is made into a coloringcomposition, the graft chain shows excellent interaction with thesolvent, and thus the uniformity of film thickness in a coating film isenhanced more.

The graft copolymer has the number of atoms except hydrogen atoms ofpreferably 40 to 10,000 per graft chain, the number of atoms excepthydrogen atoms of more preferably 100 to 500 per graft chain, and thenumber of atoms except hydrogen atoms of still more preferably 150 to260 per graft chain.

When the number of atoms except hydrogen atoms per graft chain is lessthan 40, the graft chain is short, and thus the steric repulsive effectdecreases, resulting in deteriorating the dispersibility or dispersionstability. Meanwhile, when the number of atoms except hydrogen atom pergraft chain exceeds 10,000, the graft chain is too long, and thus,adsorptivity to the colorant decreases, resulting in reducingdispersibility or dispersion stability.

Meanwhile, the number of atoms except hydrogen atoms per graft chainrefers to the number of atoms except hydrogen atoms included in a chainfrom an atom of the source bound to a polymer chain constituting themain chain to the terminal of a branched polymer branched from the mainchain. Further, when two or more kinds of graft chains are included inthe graft copolymer, it is sufficient for the number of atoms of atleast one graft chain except hydrogen atoms to satisfy the requirements.

As the polymer structure of the graft chain, a poly(meth)acrylicstructure, a polyester structure, a polyurethane structure, a polyureastructure, a polyamide structure, a polyether structure and the like maybe used. In order to improve the interaction of the graft chain with asolvent and accordingly enhance the dispersibility or dispersionstability, a graft chain including a poly(meth)acrylic structure, apolyester structure, or a polyether structure is preferred, and a graftchain including a polyester structure or a polyether structure is morepreferred.

The graft copolymer preferably has a structural unit (repeating unit)having the graft chain, and may be obtained, for example, bypolymerizing a macro monomer having a polymer structure as the graftchain based on a typical method. The structure of a macro monomer is notparticularly limited, as long as the macro monomer has a substituentcapable of reacting with the polymer main chain moiety, and also has agraft chain satisfying the requirements of the present invention.Preferably, macro monomers having a reactive double bond group may besuitably used.

Examples of commercially available macro monomers that are suitably usedfor the synthesis of the graft polymer include AA-6 (manufactured byTOAGOSEI Co., Ltd.), AA-10 (manufactured by TOAGOSEI Co., Ltd.), AB-6(manufactured by TOAGOSEI Co., Ltd.), AS-6 (manufactured by TOAGOSEICo., Ltd.), AN-6 (manufactured by TOAGOSEI Co., Ltd.), AW-6(manufactured by TOAGOSEI Co., Ltd.), AA-714 (manufactured by TOAGOSEICo., Ltd.), AY-707 (manufactured by TOAGOSEI Co., Ltd.), AY-714(manufactured by TOAGOSEI Co., Ltd.), AK-5 (manufactured by TOAGOSEICo., Ltd.), AK-30 (manufactured by TOAGOSEI Co., Ltd.), AK-32(manufactured by TOAGOSEI Co., Ltd.), BLEMMER PP-100 (manufactured byNOF Corporation), BLEMMER PP-500 (manufactured by NOF Corporation),BLEMMER PP-800 (manufactured by NOF Corporation), BLEMMER PP-1000(manufactured by NOF Corporation), BLEMMER 55-PET-800 (manufactured byNOF Corporation), BLEMMER PME-4000 (manufactured by NOF Corporation),BLEMMER PSE-400 (manufactured by NOF Corporation), BLEMMER PSE-1300(manufactured by NOF Corporation), BLEMMER 43PAPE-600B (manufactured byNOF Corporation), and the like. Among them, AA-6 (manufactured byTOAGOSEI Co., Ltd.), AA-10 (manufactured by TOAGOSEI Co., Ltd.), AB-6(manufactured by TOAGOSEI Co., Ltd.), AS-6 (manufactured by TOAGOSEICo., Ltd.), AN-6 (manufactured by TOAGOSEI Co., Ltd.), BLEMMER PME-4000(manufactured by NOF Corporation) and the like are preferred.

The graft polymer used in the present invention preferably includes, asa structure having the graft chain, at least one structural unitrepresented by any one of the following Formulas (1) to (4), and morepreferably includes at least one structural unit represented by any oneof the following Formula (1A), the following Formula (2A), the followingFormula (3A), the following Formula (3B) and the following Formula (4).

In Formulas (1) to (4), each of X¹, X², X³, X⁴ and X⁵ independentlyrepresents a hydrogen atom or a monovalent organic group. From theviewpoint of the restrictions on synthesis, a hydrogen atom or an alkylgroup having 1 to 12 carbon atoms is preferred, a hydrogen atom or amethyl group is more preferred, and a methyl group is particularlypreferred.

In Formulas (1) to (4), each of W¹, W², W³ and W⁴ independentlyrepresents an oxygen atom or NH, and an oxygen atom is particularlypreferred.

In Formulas (1) to (4), each of Y¹, Y², Y³, and Y⁴ is independently adivalent linking group, and is not particularly limited in structure.Specifically, examples thereof include linking groups from the following(Y-1) to (Y-21), and the like. In the following structures, each of Aand B represents a bond to the left terminal group and a bond to theright terminal group in Formulas (1) to (4), respectively. Among thefollowing structures, (Y-2) and (Y-13) are more preferably used due tothe simplicity of synthesis.

In formulas (1) to (4), each of Z¹, Z², Z³, and Z⁴ is independently ahydrogen atom or a monovalent substituent, and the structure of thesubstituent is not particularly limited, but specific examples thereofinclude an alkyl group, a hydroxyl group, an alkoxy group, an aryloxygroup, or a heteroaryloxy group, an alkyl thioether group, an arylthioether group, or a heteroaryl thioether group, an amino group and thelike. Among them, particularly from the viewpoint of improvingdispersibility, the group preferably has a steric repulsive effect, andas a monovalent substituent represented by Z¹ to Z³, each of the groupsis independently preferably an alkyl group having 5 to 24 carbon atomsor an alkoxy group having 5 to 24 carbon atoms, and among them, each ofthe group is independently particularly preferably an alkoxy grouphaving a branched alkyl group having 5 to 24 carbon atoms or an alkoxygroup having a cyclic alkyl group having 5 to 24 carbon atoms. Further,a monovalent substituent represented by Z⁴ is preferably an alkyl grouphaving 5 to 24 carbon atoms, and among them, each of the groups isindependently preferably a branched alkyl group having 5 to 24 carbonatoms or a cyclic alkyl group having 5 to 24 carbon atoms.

In Formulas (1) to (4), each of n, m, p, and q is an integer of 1 to500.

In Formulas (1) and (2), each of j and k is independently an integer of2 to 8. In Formulas (1) and (2), from the viewpoint of dispersionstability, j and k are preferably an integer of 4 to 6, and mostpreferably 5.

In Formula (3), R′ represents a branched or straight chained alkylenegroup. R′ in Formula (3) is preferably an alkylene group having 1 to 10carbon atoms, and more preferably an alkylene group having 2 or 3 carbonatoms.

Further, as R′ in Formula (3), two or more kinds of R's having differentstructures from one another in the dispersion resin may be mixed andused.

In Formula (4), R represents a hydrogen atom or a monovalent organicgroup, and the structure thereof is not particularly limited, butexamples thereof include preferably a hydrogen atom, an alkyl group, anaryl group, and a heteroaryl group, and more preferably a hydrogen atomand an alkyl group. When R is an alkyl group, the alkyl group ispreferably a straight chained alkyl group having 1 to 20 carbon atoms, abranched alkyl group having 3 to 20 carbon atoms, or a cyclic alkylgroup having 5 to 20 carbon atoms, more preferably a straight chainedalkyl group having 1 to 20 carbon atoms, and particularly preferably astraight chained alkyl group having 1 to 6 carbon atoms

In addition, as R in Formula (4), two or more kinds of R's havingdifferent structures from one another in the dispersion resin may bemixed and used.

As a structural unit represented by Formula (1), from the viewpoint ofdispersion stability, a structural unit represented by the followingFormula (1A) or Formula (2A) is more preferred.

In Formula (1A), X¹, Y¹, Z¹ and n have the same meanings as X¹, Y¹, Z¹and n in Formula (1), and the preferred ranges are also the same.

In Formula (2A), X², Y², Z² and m have the same meanings as X², Y², Z²and m in Formula (2), and the preferred ranges are also the same.

Further, as a structural unit represented by Formula (3), from theviewpoint of dispersion stability, a structural unit represented by thefollowing Formula (3A) or the following Formula (3B) is more preferred.

In Formula (3A) or Formula (3B), X³, Y³, Z³ and p have the same meaningsas X³, Y³, Z³ and p in Formula (3), and the preferred ranges are alsothe same.

The graft polymer more preferably has a structural unit represented byFormula (1A).

In the graft polymer used in the present invention, the structural unit(repeating unit) having the graft chain is included in a rangepreferably 10% by mass to 75% by mass, more preferably 12% by mass to50% by mass, and particularly preferably 15% by mass to 40% by mass,based on the total mass of the dispersion resin. When the amount iswithin these ranges, the dispersibility or dispersion stability of thecolorant is high, and thus the uniformity of film thickness in a coatingfilm formed by using the coloring composition is further improved.Further, the dispersion resin used in the present invention may be acombination of two or more kinds of graft copolymers whose structuresare different from one another.

In addition, in order to improve various performances such as strength,the dispersion resin in the present invention may include anotherstructural unit having further various functions, for example, astructural unit having a functional group and the like having affinityfor a dispersion medium used in a dispersoid as a structural unitderived from copolymerization components, as long as the effect of thepresent invention is not impaired.

Examples of the copolymerization components that are copolymerizablewith the dispersion resin according to the present invention include aradical polymerizable compound selected from acrylic esters, methacrylicesters, styrenes, acrylonitriles, methacrylonitriles, acrylamides,methacrylamides and the like.

Specific examples thereof include acrylic esters such as alkyl acrylate(the alkyl group preferably has 1 to 20 carbon atoms) (specifically, forexample, benzyl acrylate, 4-biphenyl acrylate, butyl acrylate, sec-butylacrylate, t-butyl acrylate, 4-t-butylphenyl acrylate, 4-chlorophenylacrylate, pentachlorophenyl acrylate, 4-cyanobenzyl acrylate,cyanomethyl acrylate, cyclohexyl acrylate, 2-ethoxyethyl acrylate, ethylacrylate, 2-ethylhexyl acrylate, heptyl acrylate, hexyl acrylate,isobornyl acrylate, isopropyl acrylate, methyl acrylate, 3,5-dimethyladamantyl acrylate, 2-naphthyl acrylate, neopentyl acrylate, octylacrylate, phenethyl acrylate, phenyl acrylate, propyl acrylate, tolylacrylate, amyl acrylate, tetrahydrofurfuryl acrylate, 2-hydroxyethylacrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl acrylate,4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, allyl acrylate,2-allyloxyethyl acrylate, propargyl acrylate and the like),

methacrylic esters such as alkyl methacrylate (the alkyl grouppreferably has 1 to 20 carbon atoms) (for example, benzyl methacrylate,4-biphenyl methacrylate, butyl methacrylate, sec-butyl methacrylate,t-butyl methacrylate, 4-t-butylphenyl methacrylate, 4-chlorophenylmethacrylate, pentachlorophenyl methacrylate, 4-cyanophenylmethacrylate, cyanomethyl methacrylate, cyclohexyl methacrylate,2-ethoxy ethyl methacrylate, ethyl methacrylate, 2-ethylhexylmethacrylate, heptyl methacrylate, hexyl methacrylate, isobornylmethacrylate, isopropyl methacrylate, methyl methacrylate, 3,5-dimethyladamantyl methacrylate, 2-naphthyl methacrylate, neopentyl methacrylate,octyl methacrylate, phenethyl methacrylate, phenyl methacrylate, propylmethacrylate, tolyl methacrylate, amyl methacrylate, tetrahydrofurfurylmethacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate,2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate,5-hydroxypentyl methacrylate, allyl methacrylate, 2-allyloxyethylmethacrylate, propargyl methacrylate, 2-diethylaminoethyl methacrylate,2-dimethylamino ethyl methacrylate and the like),

styrenes such as styrene, alkyl styrene and the like (for example,methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene,diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene,cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene,trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene andthe like), alkoxy styrene (for example, methoxy styrene,4-methoxy-3-methyl styrene, dimethoxy styrene and the like), halogenstyrene (for example, chlorostyrene, dichlorostyrene, trichlorostyrene,tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene,iodostyrene, fluorostyrene, trifluorostyrene,2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene andthe like) and acrylonitrile, methacrylonitrile.

Of these radical polymerizable compounds, methacrylic esters,acrylamides, methacrylamides and styrenes are suitably used, andexamples of particularly suitably used compounds include benzylmethacrylate, t-butyl methacrylate, 4-t-buthyphenyl methacrylate,pentachlorophenyl methacrylate, 4-cyanophenyl methacrylate, cyclohexylmethacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, isobornylmethacrylate, isopropyl methacrylate, methyl methacrylate,3,5-dimethyladamantyl methacrylate, 2-naphthyl methacrylate, neopentylmethacrylate, phenylmethacrylate, tetrahydrofurfuryl methacrylate,2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate,2-hydroxypropyl methacrylate, allyl methacrylate,

acrylamide, N-methyl acrylamide, N-isopropyl acrylamide, morpholylacrylamide, piperidyl acrylamide, N-t-butyl acrylamide, N-cyclohexylacrylamide, N-phenyl acrylamide, N-naphthyl acrylamide, N-hydroxymethylacrylamide, N-hydroxyethyl acrylamide, N-allylacrylamide,4-hydroxyphenyl acrylamide, 2-hydroxyphenyl acryl amide, N,N-dimethylacrylamide, N,N-diisopropyl acrylamide, N,N-di-t-butyl acrylamide,N,N-dicyclohexyl acrylamide, N,N-phenyl acrylamide, N,N-dihydroxyethylacrylamide, N,N-diallyl acrylamide,

methacrylamide, N-methyl methacrylamide, N-isopropyl methacrylamide,morpholyl methacrylamide, piperidyl methacrylamide, N-t-butylmethacrylamide, N-cyclohexyl methacrylamide, N-phenyl methacrylamide,N-naphthyl methacrylamide, N-hydroxymethyl methacrylamide,N-hydroxyethyl methacrylamide, N-allyl methacrylamide, 4-hydroxyphenylmethacrylamide, 2-hydroxyphenyl methacrylamide, N,N-dimethylmethacrylamide, N,N-diisopropyl methacrylamide, N,N-di-t-butylmethacrylamide, N,N-dicyclohexyl methacrylamide, N,N-phenylmethacrylamide, N,N-dihydroxyethyl methacrylamide, N,N-diallylmethacrylamide,

styrene, methyl styrene, dimethyl styrene, trimethyl styrene, isopropylstyrene, butyl styrene, cyclohexyl styrene, chloromethyl styrene,trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene,methoxy styrene, 4-methoxy-3-methyl styrene, chlorostyrene,dichlorostyrene, trichlorostyrene, tetrachlorostyrene,pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene,fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethyl styrene, and4-fluoro-3-trifluoromethyl styrene.

The radical polymerizable compounds may be used either alone or incombination of two or more thereof. The dispersion resin may or may notcontain the above-described radical polymerizable compounds, but whenthe resin contains the compound, the content of a structural unitcorresponding to the radical polymerizable compounds is from 0.1% bymass to 50% by mass and particularly preferably from 0.1% by mass to 30%by mass, based on the total mass of the dispersion resin.

The dispersion resin in the present invention may be synthesized by amethod known in the related art. Examples of solvents used in thesynthesis include ethylene dichloride, cyclohexanone, methyl ethylketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycolmonomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethylacetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,N-dimethylformamide, N,N-dimethyl acetamide, dimethyl sulfoxide, toluene, ethylacetate, methyl lactate, ethyl lactate and the like. These solvents maybe used alone or in mixture of two or more thereof.

Specifically preferred examples of the dispersion resin in the presentinvention include the following Exemplary Compounds 1 to 7, but thepresent invention is not limited thereto. Among the following ExemplaryCompounds, the numerical value written in each of the structural units(numerical value written in the repeating units of the main chain)represents a content of the structural unit [in % by mass (wt %)]. Thenumerical value added in the repeating moiety of the side chainsrepresents a repeat number of the repeating moiety.

Further, it is also preferred that the dispersion resin is a form of aresin (B1) having a repeating unit which has a group X having afunctional group with pKa of 14 or less and an oligomer chain or polymerchain Y having the number of atoms of from 40 to 10,000 in the sidechain thereof and also containing a basic nitrogen atom. However, thesolid acid number of the resin (B1) is 80 mg KOH/g or less. Due to usingthe resin (B1) as a dispersion resin, resistance of a first coloredpattern, which is formed by dry eching the first colored layer to bedescribed below, to a solvent and a developer can be more improved.

Herein, the basic nitrogen atom is not particularly limited as long asthe basic nitrogen atom is a nitrogen atom showing basicity, but theresin (B 1) preferably contains a structure having a nitrogen atom witha pKb of 14 or less and more preferably contains a structure having anitrogen atom with a pKb of 10 or less.

The basic strength pKb in the present invention refers to a pKb at awater temperature of 25° C., is one of the indices to quantitativelyrepresent the intensity of a base, and is the same as the basicityconstant. The basic strength pKb and an acid strength pKa to bedescribed below have a relationship of pKb=14−pKa.

The group X having a functional group with a pKa of 14 or less is thesame as the group X as described below with respect to the resin (B).

The oligomer chain or polymer chain Y having the number of atoms of 40to 10,000, which the resin (B1) has in the side chain thereof is alsothe same as the oligomer chain or polymer chain Y having the number ofatoms of 40 to 10,000 to be described below on the resin (B).

Examples of the resin (B1) include a resin containing a repeating unitwhich has a group X having a functional group with a pKa of 14 or lessrepresented by the following formula, a repeating unit having the basicnitrogen atom represented by the following formula and a repeating unit(corresponding in sequence from the left side of a structure of thefollowing repeating unit) which has an oligomer chain or polymer chain Yhaving the number of atoms of 40 to 10,000, represented by the followingformula and the like.

In the formula, each of x, y, and z represents a polymerization molarratio of the repeating unit, and it is preferred that x is 5 to 50, y is5 to 60, and z is 10 to 90. I represents a linking number of a polyesterchain, is an integer that may form an oligomer chain or polymer chainhaving the number of atoms of 40 to 10,000, and is preferably 70 to2,000.

The resin (B 1) is preferably a resin (B2) having a repeating unit whichcontains a nitrogen atom bonded to the group X having a functional groupwith a pKa of 14 or less and an oligomer chain or polymer chain Y whichhas the number of atoms of 40 to 10,000 in the side chain thereof.

The resin (B 1) is particularly preferably a resin (B) (hereinafter,suitably referred to as “specific resin”) having (i) at least onerepeating unit containing a nitrogen atom, selected from the groupconsisting of a poly(lower alkyleneimine)-based repeating unit, apolyallylamine-based repeating unit, a polydiallylamine-based repeatingunit, a metaxylenediamine-epichlorohydrin polycondensate-based repeatingunit and a polyvinylamine-based repeating, the repeating unit having agroup X that has a functional group with a pK_(a) of 14 or less, thegroup X being bonded to the nitrogen atom, and (ii) an oligomer chain orpolymer chain Y having the number of atoms of 40 to 10,000 in the sidechain thereof.

((i) at least one repeating unit containing a nitrogen atom, selectedfrom the group consisting of a poly(lower alkyleneimine)-based repeatingunit, a polyallylamine-based repeating unit, a polydiallylamine-basedrepeating unit, a methxylenediamine-epichlorohydrin polycondensate-basedrepeating unit and a polyvinylamine-based repeating unit)

The specific resin has (i) at least one repeating unit containing anitrogen atom, selected from the group consisting of a poly(loweralkyleneimine)-based repeating unit, a polyallylamine-based repeatingunit, a polydiallylamine-based repeating unit, ametaxylenediamine-epichlorohydrin polycondensate-based repeating unitand a polyvinylamine-based repeating unit. Accordingly, the adsorptivityon the surface of the colorant is improved and interaction betweencolorant molecules may also be reduced.

The poly(lower alkyleneime) may be in a chain-shape or a mesh form.

The number average molecular weight of a main chain obtained bypolymerizing (i) at least one repeating unit containing a nitrogen atom,selected from the group consisting of a poly(lower alkyleneimine)-basedrepeating unit, a polyallylamine-based repeating unit, apolydiallylamine-based repeating unit, ametaxylenediamine-epichlorohydrin polycondensate-based repeating unitand a polyvinylamine-based repeating unit, that is, the number averagemolecular weight of a moiety except the oligomer chain or polymer chainY moiety of the side chain from the resin (B) is preferably 100 to10,000, more preferably 200 to 5,000, and most preferably 300 to 2,000.The number average molecular weight of the main chain moiety may bedetermined from a proportion of the hydrogen atom integral value of theterminal group and of the main chain moiety measured by nuclear magneticresonance spectroscopy or may be determined by the measurement of themolecular weight of the oligomer or polymer containing an amino group asa starting material.

The repeating unit (i) containing a nitrogen atom is particularlypreferably a poly(lower alkyleneimine)-based repeating unit or apolyallylamine-based repeating unit. Meanwhile, in the presentinvention, the expression “lower” used in the poly(lower alkyleneimine)indicates that the number of carbon atoms is 1 to 5, and thelower-alkyleneimine represents an alkyleneimine having 1 to 5 carbonatoms. If this structure is specified, it is preferred that the specificresin includes a structure having a repeating unit represented byFormula (I-1) and a repeating unit represented by Formula (I-2) or astructure having a repeating unit represented by Formula (II-1) and arepeating unit represented by Formula (II-2).

(Repeating unit represented by Formula (I-1) and repeating unitrepresented by Formula (I-2))

A repeating unit represented by Formula (I-1) and a repeating unitrepresented by Formula (I-2) as preferred constituting components of thespecific resin of the present invention will be described in detail.

In Formula (I-1) and Formula (I-2), each of R¹ and R² independentlyrepresents a hydrogen atom, a halogen atom or an alkyl group. Each ofa's independently represents an integer of 1 to 5. * represents alinking portion between the repeating units.

X represents a group having a functional group with a pKa of 14 or less.

Y represents an oligomer chain or polymer chain having the number ofatoms of 40 to 10,000.

It is preferred that the specific resin has a repeating unit representedby Formula (I-3) in addition to a repeating unit represented by Formula(I-1) or Formula (I-2), as a copolymerization component. By using theserepeating units in combination, the dispersion performance is furtherimproved when the resin is used as a dispersant of the colorant.

In Formula (I-3), *, R′, R² and a are the same as those of Formula(I-1).

Y′ represents an oligomer chain or polymer chain having an anion group,which has the number of atoms of 40 to 10,000.

It is possible to form the repeating unit represented by Formula (I-3)by performing a reaction by adding an oligomer or polymer having agroup, which reacts with an amine to form a salt, to a resin having aprimary or secondary amino group in the main chain moiety thereof.

In Formula (I-1), Formula (I-2) and Formula (I-3), R¹ and R² areparticularly preferably a hydrogen atom. a is preferably 2 from theviewpoint of availability of starting materials.

The specific resin may include a lower alkyleneimine as a repeatingunit, in addition to the repeating units represented by Formula (I-1),Formula (I-2) and Formula (I-3). As described above, the loweralkyleneimine represents an alkyleneimine having 1 to 5 carbon atoms.The specific resin may or may not contain such a lower alkyleneiminerepeating unit, but when the specific resin contains a loweralkyleneimine repeating unit, the lower alkyleneimine repeating unit iscontained in an amount of preferably 1% by mole to 70% by mole, and mostpreferably 3% by mole to 50% by mole, based on the entire repeating unitincluded in the specific resin. Meanwhile, to the nitrogen atom in sucha lower alkyleneimine repeating unit, the group represented by X, Y, orY′ may also be bonded. A resin which includes both the repeating unithaving a group represented by X bonded thereto and the repeating unithaving Y bonded thereto in the main chain structure is also included inthe specific resin.

The repeating unit represented by Formula (I-1) is a repeating unitcontaining a nitrogen atom to which a group X having a functional groupwith a pKa of 14 or less is bonded, and the repeating unit containing anitrogen atom is contained in an amount of preferably 1% by mole to 80%by mole, and most preferably 3% by mole to 50% by mole, based on theentire repeating units included in the specific resin, from theviewpoint of storage stability.

The repeating unit represented by Formula (I-2) is a repeating unitwhich has an oligomer chain or polymer chain having the number of atomsof 40 to 10,000, and the repeating unit is contained in an amount ofpreferably 10% by mole to 90% by mole, and most preferably 30% by moleto 70% by mole, based on the entire repeating units of the specificresin, from the viewpoint of storage stability.

Upon reviewing both the content ratios, the molar ratio of the repeatingunits (1-1):(1-2) is preferably 10:1 to 1:100, and more preferably 1:1to 1:99, from the viewpoint of dispersion stability and balance ofhydrophilicity/hydrophobicity.

Meanwhile, the repeating unit represented by Formula (I-3), which isused in combination, as desired, is a repeating unit in which a partialstructure including an oligomer chain or polymer chain having the numberof atoms of 40 to 10,000 is ionically bonded to a nitrogen atom of themain chain, and is contained in an amount of preferably 0.5% by mole to20% by mole and most preferably 1% by mole to 10% by mole, based on theentire repeating units of the specific resin, from the viewpoint of theeffect.

Meanwhile, the ionic bond of the polymer chain Y may be confirmed byinfrared spectroscopy, or base titration.

(Repeating unit represented by Formula (II-1) and repeating unitrepresented by Formula (II-2))

A repeating unit represented by Formula (II-1) and a repeating unitrepresented by Formula (II-2) as other preferred constituting componentsof the specific resin will be described in detail.

In Formula (II-1) and Formula (II-2), each of R³, R⁴, R⁵ and R⁶independently represents a hydrogen atom, a halogen atom and an alkylgroup. *, X, and Y are the same as *, X, and Y in Formula (I-1) andFormula (I-2).

It is preferred that the specific resin includes a repeating unitrepresented by Formula (II-3) in addition to the repeating unitrepresented by Formula (II-1) and the repeating unit represented byFormula (II-2), as a copolymerization component. By using theserepeating units in combination, the dispersion performance is furtherimproved when the resin is used as a dispersant of the colorant.

In Formula (II-3), *, R³, R⁴, R⁵ and R⁶ are the same as those of Formula(II-1). Y′ are the same as Y′ in Formula (I-3).

In Formula (II-1), Formula (II-2) and Formula (II-3), R³, R⁴, R⁵ and R⁶are preferably a hydrogen atom from the viewpoint of availability ofstarting materials.

Formula (II-1) is a repeating unit containing a nitrogen atom to which agroup X having a functional group with a pKa of 14 or less is bonded,and the repeating unit containing a nitrogen atom is contained in anamount of preferably 1% by mole to 80% by mole, and most preferably 3%by mole to 50% by mole, based on all of the repeating units included inthe specific resin, from the viewpoint of storage stability.

Formula (II-2) is a repeating unit which has an oligomer chain orpolymer chain Y having the number of atoms of 40 to 10,000, and therepeating unit is contained in an amount of preferably 10% by mole to90% by mole and most preferably 30% by mole to 70% by mole, based on allof the repeating units of the specific resin, from the viewpoint ofstorage stability.

Upon reviewing both the content ratios, the molar ratio of the repeatingunits (II-1):(II-2) is preferably 10:1 to 1:100, and more preferably 1:1to 1:10, from the viewpoint of dispersion stability and balance ofhydrophilicity/hydrophobicity.

The repeating unit represented by Formula (II-3), which is used incombination, as desired, is contained in an amount of preferably 0.5% bymole to 20% by mole, and most preferably 1% by mole to 10% by mole,based on all of the repeating units of the resin of the presentinvention.

In the specific resin, it is most preferred to include particularly botha repeating unit represented by Formula (I-1) and a repeating unitrepresented by Formula (I-2) from the view point of dispersibility.

<Group X Having Functional Group with pKa of 14 or Less>

X has a functional group with a pKa of 14 or less at a water temperatureof 25° C. The “pKa” as mentioned herein is the definition as describedin Chemical Handbook (II) (4^(th) Revised Edition, 1993, edited by TheChemical Society of Japan, Maruzen Co., Ltd.).

The “functional group with a pKa of 14 or less” is not particularlylimited in structure and the like as long as the physical propertiesthereof satisfy this condition, and examples thereof include knownfunctional groups with a pKa satisfying the above-described range, but afunctional group having a pKa of 12 or less is particularly preferredand a group having a pKa of 11 or less is most preferred. Specificexamples thereof include carboxylic acid (pKa of approximately 3 to 5),sulfonic acid (pKa of approximately −3 to −2), —COCH₂CO— (pKa ofapproximately 8 to 10), —COCH₂CN (pKa of approximately 8 to 11),—CONHCO—, a phenolic hydroxyl group, —R_(F)CH₂OH or —(R_(F))₂CHOH(R_(F)represents a perfluoroalkyl group. pKa of approximately 9 to 11), asulfonamide group (pKa of approximately 9 to 11) and the like, andcarboxylic acid (pKa of approximately 3 to 5), sulfonic acid (pKa ofapproximately −3 to −2), and —COCH₂CO— (pKa of approximately 8 to 10)are particularly preferred.

The pKa of a functional group in the group X is 14 or less, and thus,interaction between the group and the colorant may be achieved.

It is preferred that the group X having a functional group with a pKa of14 or less is directly bonded to a nitrogen atom in the repeating unitcontaining the nitrogen atom, but the nitrogen atom of the repeatingunit containing the nitrogen atom and the group X may be linked throughcovalent bonding as well as through ionic bonding to form a salt.

It is particularly preferred that the group X containing a functionalgroup with a pKa of 14 or less in the present invention has a structurerepresented by Formula (V-1), Formula (V-2), or Formula (V-3).

In Formula (V-1) and Formula (V-2), U represents a single bond or adivalent linking group.

Each of d and e independently represents 0 or 1.

In Formula (V-3), Q represents an acyl group or an alkoxycarbonyl group.

Examples of the divalent linking group represented by U include alkylene(more specifically, for example, —CH₂—, —CH₂CH₂—, —CH₂CHMe-, —(CH₂)₅—,—CH₂CH(n-C₁₀H₂₁)— and the like), an oxygen-containing alkylene (morespecifically, for example, —CH₂OCH₂—, —CH₂CH₂OCH₂CH₂— and the like), anarylene group (for example, phenylene, tolylene, biphenylene,naphthylene, furanylene, pyrrolylene and the like), alkyleneoxy (forexample, ethyleneoxy, propyleneoxy, phenyleneoxy and the like), analkenylene group (for example, a vinylene group) and the like. Amongthem, an alkylene group having 1 to 30 carbon atoms, or an arylene grouphaving 6 to 20 carbon atoms is particularly preferred, and alkylenehaving 1 to 20 carbon atoms, alkenylene having 2 to 20 carbon atoms orarylene having 6 to 15 carbon atoms is most preferred. Further, from theviewpoint of productivity, d is preferably 1, and e is preferably 0.

Q represents an acyl group or an alkoxycarbonyl group. As the acyl groupin Q, an acyl group having 1 to 30 carbon atoms (for example, formyl,acetyl, n-propanoyl, benzoyl and the like) is preferred, and acetyl isparticularly preferred. As the alkoxycarbonyl group in Q, analkoxycarbonyl group having 2 to 30 carbon atoms (for example, amethoxycarbonyl group, an ethoxycarbonyl group, n-propoxycarbonyl groupand the like) is preferred. As Q, an acyl group is particularlypreferred, and an acetyl group is preferred from the viewpoint of easein preparation and availability of starting materials (precursor X′ ofX).

The group X in the present invention is preferably bonded to a nitrogenatom of the repeating unit that contains the nitrogen atom. By such astate, the dispersibility and dispersion stability of the colorant isdrastically improved. The reason is not clear, but it is thought asfollows. That is, it is thought that the nitrogen atom of the repeatingunit containing the nitrogen atom exists as a structure of an aminogroup, an ammonium group or an amide group, and the groups haveinteraction, such as hydrogen bonding and ionic bonding, with an acidicportion on the colorant surface, to be adsorbed to each other. Inaddition, the X in the present invention functions as an acid group, andthus, may show stronger interaction when the colorant shows basicity.That is, it is thought that the specific resin may adsorb both the basicportion and the acidic portion of the colorant with the nitrogen atomand the group X, such that the adsorption capacity is increased, therebydrastically improving the dispersibility and storage stability.

Furthermore, it is thought that the X in the present invention impartsthe solvent solubility to suppress resins from being precipitated overtime, thereby contributing to dispersion stability.

The content of the functional group with a pKa of 14 or less in X is notparticularly limited, but is preferably 0.01 mmol to 5 mmol, and mostpreferably 0.05 mmol to 1 mmol, based on 1 g of the specific resin.Within this range, the dispersiblity and dispersion stability of thecolorant are improved.

(Oligomer chain or polymer chain Y having number of atoms of 40 to10,000)

Examples of Y include known polymer chains such as polyester, polyamide,polyimide and poly(meth)acrylic acid ester, which may be linked to themain chain moiety of the specific resin. The binding site of Y to thespecific resin is preferably a terminal end of the oligomer chain orpolymer chain Y.

Y is preferably bonded to a nitrogen atom of at least one repeating unitcontaining the nitrogen atom, selected from a poly(loweralkyleneimine)-based repeating unit, a polyallylamine-based repeatingunit, a polydiallylamine-based repeating unit, amethxylenediamine-epichlorohydrin polycondensate-based repeating unitand a polyvinylamine-based repeating unit. The bonding mode between Yand the main chain moiety such as at least one repeating unit containinga nitrogen atom, selected from a poly(lower alkyleneimine)-basedrepeating unit, a polyallylamine-based repeating unit, apolydiallylamine-based repeating unit, ametaxylenediamine-epichlorohydrin polycondensate-based repeating unitand a polyvinylamine-based repeating unit is covalent bonding, ionicbonding, or a combination of covalent bonding and ionic bonding. Theratio of the bonding modes of Y and the main chain moiety is in a rangeof covalent bonding:ionic bonding=100:0 to 0:100, but is preferably 95:5to 5:95 and most preferably 90:10 to 10:90. When the ratio is out of therange, the dispersibility and dispersion stability are deteriorated andthe solvent solubility is also decreased.

To the nitrogen atom of the repeating unit that contains the nitrogenatom, Y is preferably amide-bonded, or ionically bonded as carboxylate.

The number of atoms of the oligomer chain or polymer chain Y ispreferably 50 to 5,000, and more preferably 60 to 3,000, from theviewpoint of dispersibility and dispersion stability.

When the number of atoms per the oligomer chain or polymer chain Y isless than 40, the graft chain is short, and thus the steric repulsiveeffect is decreased, resulting in reducing the dispersibility.Meanwhile, when the number of atoms per the oligomer chain or polymerchain Y exceeds 10,000, the oligomer chain or polymer chain Y is toolong, and thus adsorptivity to the colorant is decreased, resulting inreducing the dispersibility.

Further, the number average molecular weight of Y may be measured by apolystyrene converted value by a GPC method. The number averagemolecular weight of Y is particularly preferably 1,000 to 50,000, andmost preferably 1,000 to 30,000 from the viewpoint of dispersibility anddispersion stability.

Preferably two or more, and most preferably five or more of the sidechain structures represented by Y are bonded to the main chain linkagein one molecule of the resin.

In particular, Y preferably has a structure represented by Formula(III-1).

In Formula (III-1), Z is a polymer or oligomer having a polyester chainas a partial structure, and represents a residue except the carboxylgroup from a polyester having a free carboxyl acid represented by thefollowing Formula (IV).

In Formula (IV), Z is the same as Z in Formula (III-1).

When the specific resin contains a repeating unit represented by Formula(I-3) or Formula (II-3), Y′ is preferably Formula (III-2).

In Formula (III-2), Z is the same as Z in Formula (III-1).

A polyester having a carboxyl group at one end (polyester represented byFormula (IV)) may be obtained by polycondensation (IV-1) of carboxylicacid and lactone, polycondensation (IV-2) of a hydroxy group-containingcarboxylic acid, polycondensation (IV-3) of a dihydric alcohol and adivalent carboxylic acid (or a cyclic acid anhydride) and the like.

The carboxylic acid used in the polycondensation reaction (IV-1) ofcarboxylic acid and lactone may be an aliphatic carboxylic acid(preferably straight chained or branched carboxylic acid having 1 to 30carbon atoms, for example, formic acid, acetic acid, propionic acid,butyric acid, valeric acid, n-hexanoic acid, n-octanoic acid, n-decanoicacid, n-dodecanoic acid, palmitic acid, 2-ethylhexanoic acid,cyclohexanoic acid and the like), a hydroxy group-containing carboxylicacid (preferably a straight chained or branched hydroxy group-containingcarboxylic acid having 1 to 30 carbon atoms, for example, glycolic acid,lactic acid, 3-hydroxypropionic acid, 4-hydroxydodecanoic acid,5-hydroxydodecanoic acid, ricinoleic acid, 12-hydroxydodecanoic acid,12-hydroxystearic acid and 2,2-bis(hydroxymethyl)butyric acid and thelike), but particularly preferably a straight chained aliphaticcarboxylic acid having 6 to 20 carbon atoms or a hydroxygroup-containing carboxylic acid having 1 to 20 carbon atoms. Thesecarboxylic acids may be used in a mixture thereof. As the lactone, aknown lactone may be used, and examples thereof include β-propiolactone,β-butyrolactone, γ-butyrolactone, γ-hexanolactone, γ-octanolactone,δ-valerolactone, δ-hexanolactone, δ-octanolactone, ε-caprolactone,δ-dodecanolactone, α-methyl-γ-butyrolactone and the like, andε-caprolactone is particularly preferred from the viewpoint ofreactivity and availability.

These lactones may be used in a mixture of plural kinds thereof.

The feed molar ratio of the carboxylic acid and the lactone at the timeof the reaction depends on the molecular weight of a target polyesterchain, and thus may not be exclusively determined, but is preferablycarboxylic acid:lactone=1:1 to 1:1,000, and most preferably 1:3 to1:500.

The hydroxy group-containing carboxylic acid in the polycondensation(IV-2) of the hydroxy group-containing carboxylic acid is the same asthe hydroxy group-containing carboxylic acid in (IV-1), and thepreferred ranges thereof are also the same.

The dihydric alcohol in the polycondensation reaction (IV-3) of thedihydric alcohol and divalent carboxylic acid (or cyclic acid anhydride)may be a straight chained or branched aliphatic diol (preferably a diolhaving 2 to 30 carbon atoms, for example, ethylene glycol, diethyleneglycol, triethylene glycol, dipropylene glycol, 1,2-propanediol,1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol and thelike), and particularly preferably an aliphatic diol having 2 to 20carbon atoms.

Examples of the divalent carboxylic acid include a straight chained orbranched divalent aliphatic carboxylic acid (preferably a divalentaliphatic carboxylic acid having 1 to 30 carbon atoms, for example,succinic acid, maleic acid, adipic acid, sebacic acid, dodecanoicdiacid, glutaric acid, suberic acid, tartaric acid, oxalic acid, malonicacid and the like), and a divalent carboxylic acid having 3 to 20 carbonatoms is particularly preferred. Further, acid anhydride (for example,succinic anhydride, glutaric anhydride and the like), which areequivalent to these divalent carboxylic acids, may also be used.

The divalent carboxylic acid and the dihydric alcohol are preferably fedat a molar ratio of 1:1. Accordingly, it is possible to introducecarboxylic acid into a terminal end.

The polycondensation at the time of preparation of polyester ispreferably carried out with the addition of a catalyst. The catalyst ispreferably a catalyst which functions as a Lewis acid, and examplesthereof include a Ti compound (for example, Ti(OBu)₄, Ti(O-Pr)₄ and thelike), an Sn compound (for example, tin octylate, dibutyltin oxide,dibutyltin laurate, monobutyltin hydroxybutyl oxide, stannic chlorideand the like), protonic acid (for example, sulfuric acid,paratoluenesulfonic acid and the like) and the like. The amount of thecatalyst is preferably 0.01% by mole to 10% by mole, and most preferably0.1% by mole to 5% by mole, based on the number of moles of all of themonomers. The reaction temperature is preferably 80° C. to 250° C., andmost preferably 100° C. to 180° C. The reaction time varies depending onthe reaction condition, but is usually 1 hour to 24 hours.

The number average molecular weight of the polyester may be measured bya polystyrene converted value by a GPC method. The number averagemolecular weight of the polyester is 1,000 to 1,000,000, preferably2,000 to 100,000, and most preferably 3,000 to 50,000. When themolecular weight is within the range, the dispersiblity is moreimproved.

The polyester partial structure forming a polymer chain in Y ispreferably polyester, obtained by particularly the polycondensation(IV-1) of carboxylic acid and lactone, and the polycondensation (IV-2)of a hydroxy group-containing carboxylic acid, from the viewpoint ofease in preparation.

The specific embodiments [(A-1) to (A-61)] of the specific resin areshown below by the specific structures of the repeating units which theresin has and the combinations thereof, but the present invention is notlimited thereto. In the following formulas, each of k, l, m, and nrepresents a polymerization molar ratio of the repeating unit, k is 1 to80, l is 10 to 90, m is 0 to 80, n is 0 to 70, and also k+l+m+n=100. pand q represent a linking number of a polyester chain, and each of p andq independently represents 5 to 100,000. R represents a hydrogen atom oran alkylcarbonyl group.

X (A-1)

(A-2)

(A-3)

(A-4)

(A-5)

(A-6)

(A-7)

(A-8)

(A-9)

(A-10)

(A-11)

(A-12)

(A-13)

(A-14)

(A-15)

X (A-16)

(A-17)

(A-18)

(A-19)

(A-20)

(A-21)

(A-22)

(A-23)

(A-24)

(A-25) —CH₂CO₂H (A-26) —CH₂CH₂CO₂H (A-27)

(A-28)

Y (A-29)

(A-30)

(A-31)

(A-32)

(A-33)

(A-34)

(A-35)

Y (A-36)

(A-37)

(A-38)

(A-39)

(A-40)

(A-41)

(A-42)

Y (A-43)

(A-44)

(A-45)

(A-46)

(A-47)

(A-48)

(A-49)

(A-50)

(A-51)

(A-52)

(A-53)

(A-54)

(A-55)

(A-56)

(A-57)

(A-58)

(A-59)

(A-60)

(A-61)

In order to synthesize the specific resin, the specific resin may beprepared by (1) a method for reacting a resin having a primary orsecondary amino group, a precursor x of X and a precursor y of Y, (2) amethod by polymerizing a monomer containing X and a macromonomercontaining Y, and the like, but the specific resin is preferablyprepared by first synthesizing a resin having a primary or secondaryamino group in the main chain, and then allowing the resin to undergo areaction with the precursor x of X and the precursor y of Y to introducethe reaction products into a nitrogen atom present in the main chain bya polymer reaction.

Examples of the resin having a primary or secondary amino group includean oligomer or polymer containing a primary or secondary amino group,which constitutes the main chain moiety having a nitrogen atom, and forexample, poly(lower alkyleneimine), polyallylamine, polydiallylamine, ametaxylenediamine-epichlorohydrin polycondensate, polyvinylamine and thelike. Among them, an oligomer or polymer including poly(loweralkyleneimine) or polyallylamine is preferred.

The precursor x of the group X having a functional group with a pKa of14 or less represents a compound which may react with the resin having aprimary or secondary amino group to introduce X into the main chain.

Examples of the x include a cyclic carboxylic anhydride (a cycliccarboxylic anhydride having 4 to 30 carbon atoms is preferred, and forexample, succinic anhydride, glutaric anhydride, itaconic anhydride,maleic anhydride, allylsuccinic anhydride, butylsuccinic anhydride,n-octylsuccinic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinicanhydride, n-tetradecylsuccinic anhydride, n-dococenylsuccinicanhydride, (2-hexen-1-yl)succinic anhydride,(2-methylpropen-1-yl)succinic anhydride, (2-dodecen-1-yl)succinicanhydride, n-octenyl succinic anhydride, (2,7-octanedien-1-yl)succinicanhydride, acetylmalic anhydride, diacetyltartaric anhydride, heticanhydride, cyclohexane-1,2-dicarboxylic anhydride, 3- or4-methylcyclohexane-1,2-dicarboxylic anhydride, tetrafluorosuccinicanhydride, 3- or 4-cyclohexene-1,2-dicarboxylic anhydride,4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, phthalic anhydride,tetrachlorophthalic anhydride, naphthalic anhydride,bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride,pyromellitic dianhydride, meso-butane-1,2,3,4-tetracarboxylicdianhydride, 1,2,3,4-cyclopentane carboxylic dianhydride and the like),halogen atom-containing carboxylic acid (for example, chloroacetic acid,bromoacetic acid, iodoacetic acid, 4-chloro-n-butyric acid and thelike), sultone (for example, propanesultone, 1,4-butanesultone and thelike), diketone, a cyclic sulfocarboxylic acid anhydride (for example,2-sulfobenzoic acid anhydride and the like), a —COCH₂COCl-containingcompound (for example, ethylmalonyl chloride and the like), or a cyanoacetic acid chloride and the like, and a cyclic carboxylic acidanhydride, sultone and diketone are particularly preferred from theviewpoint of productivity.

The precursor y of the oligomer chain or polymer chain Y having thenumber of atoms of 40 to 10,000 represents a compound which may reactwith resin having a primary or secondary amino group to introduce theoligomer chain or polymer chain Y.

The y is preferably an oligomer or polymer having the number of atoms of40 to 10,000 and having a group, that may be covalently or ionicallybonded to a nitrogen atom of the specific resin, at a terminal end, andparticularly, an oligomer or polymer having the number of atoms of 40 to10,000 and having a free carboxyl group at one end is most preferred.

Examples of y include a polyester represented by Formula (IV), which hasa free carboxyl acid at one end, a polyamide which has a free carboxylacid at one end, a poly(meth)acrylic acid-based resin which has a freecarboxyl acid at one end and the like, but particularly, a polyesterrepresented by Formula (IV), which contains a free carboxyl acid at oneend, is most preferred.

The y may be synthesized by a known method, for example, a polyestercontaining a free carboxyl acid at one end, which is represented byFormula (IV) is formed by the polycondensation (IV-1) of carboxylic acidand lactone, the polycondensation (IV-2) of a hydroxy group-containingcarboxylic acid or the polycondensation (IV-3) of a dihydric alcohol anda divalent carboxylic acid (or a cyclic acid anhydride) as describedabove. The polyamide containing a free carboxyl acid at one end may beprepared by self-condensation of an amino group-containing carboxylicacid (for example, glycine, alanine, (3-alanine, 2-aminobutyric acid andthe like) and the like. The poly(meth)acrylic acid ester having a freecarboxyl acid at one end may be prepared by radical polymerization of(meth)acrylic acid-based monomers in the presence of a carboxylgroup-containing chain transfer agent (for example, 3-mercaptopropionicacid and the like).

The specific resin may be prepared by (a) a method in which a resinhaving a primary or secondary amino group, x and y are simultaneouslyreacted with each other, (b) a method in which a resin having a primaryor secondary amino group is first reacted with x, and then reacted withy or (c) a method in which a resin having a primary or secondary aminogroup is first reacted with y, and then reacted with x. In particular,(c) a method in which a resin having a primary or secondary amino groupis first reacted with y, and then reacted with x is preferred.

The reaction temperature may be suitably selected according to theconditions, but is preferably 20° C. to 200° C., and most preferably 40°C. to 150° C. The reaction time is preferably 1 hour to 48 hours, andmore preferably 1 hour to 24 hours from the viewpoint of productivity.

The reaction may be carried out in the presence of a solvent. Examplesof the solvent include water, a sulfoxide compound (for example,dimethylsulfoxide and the like), a ketone compound (for example,acetone, methyl ethyl ketone, cyclohexanone and the like), an estercompound (for example, ethyl acetate, butyl acetate, ethyl propionate,propylene glycol 1-monomethyl ether 2-acetate and the like), an ethercompound (for example, diethyl ether, dibutyl ether, tetrahydrofuran andthe like), an aliphatic hydrocarbon compound (for example, pentane,hexane and the like), an aromatic hydrocarbon compound (for example,toluene, xylene, mesitylene and the like), a nitrile compound (forexample, acetonitrile, propionitrile and the like), an amide compound(for example, N,N-dimethyl formamide, N,N-dimethylacetamide,N-methylpyrrolidone and the like), a carboxylic acid compound (forexample, acetic acid, propionic acid and the like), an alcohol compound(for example, methanol, ethanol, isopropanol, n-butanol, 3-methylbutanol, 1-methoxy-2-propanol and the like) and a halogen-based solvent(for example, chloroform, 1,2-dichloroethane and the like).

When a solvent is used, the solvent is preferably used at 0.1 times bymass to 100 times by mass, and most preferably 0.5 times by mass to 10times by mass, based on a substrate.

The specific resin may be purified by a reprecipitation method. When thespecific resin obtained by removing low molecular weight components bythe reprecipitation method is used as a dispersant, the dispersionperformance is improved.

For the reprecipitation, a hydrocarbon-based solvent such as hexane andan alcohol-based solvent such as methanol are preferably used.

Hereinafter, specific examples of the specific resin will be describedalong with the molecular weights thereof. R′ represents an alkyl group.

k/(l1+l2)/(m1+m2)/n=10/50/5/35 x+y=40 Mw 24,000 Mw/Mn=1.6

k/(l1+l2)/(m1+m2)/n=20/4/5/35 x+y=60 Mw 18,000 Mw/Mn=1.6

k/(l1+l2)/(m1+m2)/n=5/60/10/25 x+y=20 Mw 12,000 Mw/Mn=1.6

k/(l1+l2)/(m1+m2)/n=10/50/5/35 x+y=40 Mw 24,000 Mw/Mn=1.6

k/(l1+l2)/(m1+m2)/n=30/60/5/5 Mw 40,000 Mw/Mn=2.5 x+y=20

k(l1+l2)/(m1+m2)/n=20/70/5/5 Mw 42,000 Mw/Mn=2.5 x+y=40

k/l/n=10/64/26 Mw 32,000 Mw/Mn=1.6 p=5˜100000

k/l/m/n=25/41/4/30 p=60 Mw 9,000 Mw/Mn=2.1

A binder resin is often added during the preparation of a pigmentdispersion liquid, does not need alkali solubility, and is soluble onlyin an organic solvent.

As the binder, a linear organic high polymer which is soluble in anorganic solvent is preferred. Examples of the linear organic highpolymer include polymers having carboxylic acid at the side chainthereof, and methacrylic acid copolymers, acrylic acid copolymers,itaconic acid copoymers, crotonic acid copolymers, maleic acidcopolymers, partially esterified maleic acid copolymers and the like asdescribed in, for example, Japanese Patent Publication No. S59-44615,Japanese Patent Publication No. S54-34327, Japanese Patent PublicationNo. S58-12577, Japanese Patent Publication No. S54-25957, JapanesePatent Application Laid-Open No. S59-53836 and Japanese PatentApplication Laid-Open No. S59-71048, and an acidic cellulose derivativehaving carboxylic acid similarly at the side chain thereof is alsouseful.

Among these various binders, polyhydroxystyrene-based resins,polysiloxane-based resins, acrylic resins, acrylamide-based resins andacrylic/acrylamide copolymer resins are preferred from the viewpoint ofheat resistance, and acrylic resins, acrylamide-based resins andacrylic/acrylamide copolymer resins are more preferred.

As the acrylic resin, copolymers including a monomer selected frombenzyl (meth)acrylate, (meth)acrylic acid, hydroxyethyl (meth)acrylate,(meth)acrylamide and the like, for example, each copolymer such asbenzyl methacrylate/methacrylic acid and benzyl methacrylate/benzylmethacrylamide, KS RESIST-106 (manufactured by Osaka Organic ChemicalIndustry Ltd.) and CYCLOMER-P SERIES (manufactured by DaicelCorporation) are preferred.

Adhesion to the lower layer and the like may be imparted by dispersingthe above-mentioned colorant in these binders at high concentration, andthese binders also contribute to the coated surface shape duringspin-coating and slit-coating (formation of a colored layer).

The weight average molecular weight of the resin in the presentinvention (a polystyrene converted value measured by GPC method) ispreferably 5,000 to 300,000, more preferably 7,000 to 100,000, andparticularly preferably 10,000 to 50,000.

In particular, the specific resin as a dispersion resin has a weightaverage molecular weight of 3,000 to 100,000, and more preferably 5,000to 55,000, as measured by a GPC method. The molecular weight in theabove-described range is advantageous in that high storage stability maybe achieved. Further, the presence of a nitrogen atom in (i) therepeating unit containing the nitrogen atom in the specific resin of thepresent invention may be confirmed by a method such as acid titration,and the presence of a functional group having a pKa of 14 or less andthe bonding of the functional group to the nitrogen atom of therepeating unit may be confirmed by a method such as base titration,nuclear magnetic resonance spectroscopy and infrared spectroscopy. Inaddition, the fact that the specific resin has (ii) an oligomer chain orpolymer chain Y having 40 to 10,000 atoms as a side chain may beconfirmed by a method such as nuclear magnetic resonance spectroscopyand a GPC method.

In the coloring composition of the present invention, the resins may beused either alone or in combination of two or more thereof.

In addition, examples of the resin also include resins in which acurable compound to be described below is a polymer compound and resinsin which a surfactant to be described below is a polymer compound.

The content of the resin is preferably 10% by mass to 50% by mass, morepreferably 11% by mass to 40% by mass, and still more preferably 12% bymass to 30% by mass, based on the total solids of the coloringcomposition of the present invention.

[3] Curable Compound

The coloring composition of the present invention preferably contains atleast one of curable compounds.

As the curable compound, a compound, which may be subjected to filmcuring by heating, is preferred, and for example, a compound having aheat curable functional group may be used. The heat curable compoundpreferably has at least one group selected from, for example, an epoxygroup, a methylol group, an alkoxymethyl group, an acyloxymethyl group,a (meth)acryloyl group, an isocyanate group, a vinyl group and amercapto group, as the heat curable functional group. As the heatcurable compound, a heat curable compound having two or more heatcurable functional groups per a molecular is preferred.

More preferred examples thereof include an epoxy resin, analkoxymethylated or acyloxymethylated melamine compound or resin, analkoxymethylated or acyloxymethylated urea compound or resin, ahydroxymethylated or alkoxymethylated phenol compound or resin, analkoxymethyl-etherified phenol compound or resin and the like.

Particularly preferred examples of the curable compounds include aphenol derivative having a molecular weight of 1,200 or less, includingfrom three to five benzene rings in the molecule and further having twoor more hydroxymethyl groups or alkoxymethyl groups in total, in whichthe hydroxymethyl groups or alkoxymethyl groups are concentrated to atleast any one benzene ring or classified and bonded. By using such aphenol derivative, the effects of the present invention may be moreremarkably brought out. The alkoxymethyl group bonded to the benzenering preferably has 6 or less carbon atoms. Specifically, amethoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, ani-propoxymethyl group, an n-butoxymethyl group, an i-butoxymethyl group,a sec-butoxymethyl group and a t-butoxymethyl group are preferred.Further, an alkoxy-substituted alkoxy group such as a 2-methoxyethoxygroup and a 2-methoxy-1-propoxy group is also preferred.

The curable compound is preferably a phenol compound having a benzenering in the molecule and more preferably a phenol compound having two ormore benzene rings in the molecule, and is preferably a phenol compoundcontaining no nitrogen atom.

The curable compound is preferably a phenol compound having from two toeight heat curable functional groups per molecule, and more preferablyhas from three to six heat curable functional groups.

Among these phenol derivatives, particularly preferred compounds areexemplified below. In the formulas, each of L¹ to L⁸ represents a heatcurable functional group such as an alkoxymethyl group, and may be thesame as or different from every other L¹ to L⁸, and the heat curablefunctional group is preferably a hydroxymethyl group, a methoxymethylgroup or an ethoxymethyl group

As the curable compound, a commercially available product may be used,or the compound may be synthesized by a known method. For example, aphenol derivative having a hydroxymethyl group may be obtained byreacting a phenol compound having no hydroxymethyl group (in theformula, a compound in which each of L¹ to L₈ is a hydrogen atom) withformaldehyde in the presence of a base catalyst. At this time, in orderto prevent resinification or gelling, the reaction is preferablyperformed at a temperature of 60° C. or less. Specifically, thisderivative may be synthesized by the method as described in JapanesePatent Application Laid-Open No. H6-282067, Japanese Patent ApplicationLaid-Open No. H7-64285 and the like.

A phenol derivative having an alkoxymethyl group may be obtained byreacting a phenol derivative having a hydroxymethyl group with analcohol in the presence of an acid catalyst. At this time, in order toprevent resinification or gelling, the reaction is preferably performedat a temperature of 100° C. or less. Specifically, this derivative maybe synthesized by the method as described in EP632003A1 and the like.The thus-synthesized phenol derivative having a hydroxymethyl group oran alkoxymethyl group is preferred from the viewpoint of stabilityduring storage, but a phenol derivative having an alkoxymethyl group isparticularly preferred from the viewpoint of stability during storage.These phenol derivatives having two or more hydroxymethyl groups oralkoxymethyl groups in total that are concentrated to at least any onebenzene ring or classified and bonded, may be used either alone or incombination of two or more thereof.

In addition, the curable compound also includes (i) a compound having anN-hydroxymethyl group, an N-alkoxymethyl group or an N-acyloxymethylgroup and (ii) an epoxy compound, as described below.

(i) The compound having an N-hydroxymethyl group, an N-alkoxymethylgroup or an N-acyloxymethyl group is preferably a compound having two ormore (more preferably from two to eight) partial structures representedby the following Formula (CLNM-1).

In Formula (CLNM-1), R^(NM1) represents a hydrogen atom, an alkyl group,a cycloalkyl group or an oxoalkyl group.

The alkyl group of R^(NM1) in Formula (CLNM-1) is preferably a straightchained or branched alkyl group having 1 to 6 carbon atoms. Thecycloalkyl group of R^(NM1) is preferably a cycloalkyl group having 5 to6 carbon atoms. The oxoalkyl group of R^(NM1) is preferably an oxoalkylgroup having 3 to 6 carbon atoms, and examples thereof include aβ-oxopropyl group, a β-oxobutyl group, a β-oxopentyl group, a β-oxohexylgroup and the like.

More preferred aspects of the compound having two or more partialstructures represented by Formula (CLNM-1) include a urea-basedcrosslinking agent represented by the following Formula (CLNM-2), analkylene urea-based crosslinking agent represented by the followingFormula (CLNM-3), a glycoluril-based crosslinking agent represented bythe following Formula (CLNM-4) and a melamine-based crosslinking agentrepresented by the following Formula (CLNM-5).

In Formula (CLNM-2), each R^(NM1) independently is the same as R^(NM1)in Formula (CLNM-1).

Each R^(NM2) independently represents a hydrogen atom, an alkyl group(preferably having 1 to 6 carbon atoms) or a cycloalkyl group(preferably having 5 to 6 carbon atoms).

Specific examples of the urea-based crosslinking agent represented byFormula (CLNM-2) include N,N-di(methoxymethyl)urea,N,N-di(ethoxymethyl)urea, N,N-di(propoxymethyl)urea,N,N-di(isopropoxymethyl)urea, N,N-di(butoxymethyl)urea,N,N-di(t-butoxymethyl)urea, N,N-di(cyclohexyloxymethyl)urea,N,N-di(cyclopentyloxymethyl)urea, N,N-di(adamantyloxymethyl)urea,N,N-di(norbornyloxymethyl)urea and the like.

In Formula (CLNM-3), each R^(NM1) independently is the same as R^(NM1)in Formula (CLNM-1).

Each R^(NM3) independently represents a hydrogen atom, a hydroxyl group,a straight chained or branched alkyl group (preferably having 1 to 6carbon atoms), a cycloalkyl group (preferably having 5 to 6 carbonatoms), an oxoalkyl group (preferably having 1 to 6 carbon atoms), analkoxy group (preferably having 1 to 6 carbon atoms) or an oxoalkoxygroup (preferably having 1 to 6 atoms).

G represents a single bond, an oxygen atom, a sulfur atom, an alkylenegroup (preferably having 1 to 3 carbon atoms) or a carbonyl group. Morespecific examples thereof include a methylene group, an ethylene group,a propylene group, a 1-methylethylene group, a hydroxymethylene group, acyanomethylene group and the like.

Specific examples of the alkylene urea-based crosslinking agentrepresented by Formula (CLNM-3) includeN,N-di(methoxymethyl)-4,5-di(methoxymethyl)ethylene urea,N,N-di(ethoxymethyl)-4,5-di(ethoxymethyl)ethylene urea,N,N-di(propoxymethyl)-4,5-di(propoxymethyl)ethylene urea,N,N-di(isopropoxymethyl)-4,5-di(isopropoxymethyl)ethylene urea,N,N-di(butoxymethyl)-4,5-di(butoxymethyl)ethylene urea,N,N-di(t-butoxymethyl)-4,5-di(t-butoxymethyl)ethylene urea,N,N-di(cyclohexyloxymethyl)-4,5-di(cyclohexyloxymethyl)ethylene urea,N,N-di(cyclopentyloxymethyl)-4,5-di(cyclopentyloxymethyl)ethylene urea,N,N-di(adamantyloxymethyl)-4,5-di(adamantyloxymethyl)ethylene urea,N,N-di(norbornyloxymethyl)-4,5-di(norbornyloxymethyl)ethylene urea andthe like.

In Formula (CLNM-4), each R^(NM1) independently is the same as R^(NM1)in Formula (CLNM-1).

Each R^(NM4) independently represents a hydrogen atom, a hydroxyl group,an alkyl group, a cycloalkyl group or an alkoxy group.

More specific examples of the alkyl group (preferably having 1 to 6carbon atoms), cycloalkyl group (preferably having 5 to 6 carbon atoms)and alkoxy group (preferably having 1 to 6 carbon atoms) of R^(NM4)include a methyl group, an ethyl group, a butyl group, a cyclopentylgroup, a cyclohexyl group, a methoxy group, an ethoxy group, a butoxygroup and the like.

Specific examples of the glycoluril-based crosslinking agent representedby Formula (CLNM-4) include N,N,N,N-tetra(methoxymethyl)glycoluril,N,N,N,N-tetra(ethoxymethyl)glycoluril,N,N,N,N-tetra(propoxymethyl)glycoluril,N,N,N,N-tetra(isopropoxymethyl)glycoluril,N,N,N,N-tetra(butoxymethyl)glycoluril,N,N,N,N-tetra(t-butoxymethyl)glycoluril,N,N,N,N-tetra(cyclohexyloxymethyl)glycoluril,N,N,N,N-tetra(cyclopentyloxymethyl)glycoluril,N,N,N,N-tetra(adamantyloxymethyl)glycoluril,N,N,N,N-tetra(norbornyloxymethyl)glycoluril and the like.

In Formula (CLNM-5), each R^(NM1) independently is the same as R^(NM1)in Formula (CLNM-1).

Each R^(NM5) independently represents a hydrogen atom, an alkyl group, acycloalkyl group, an aryl group or an atomic group represented by thefollowing Formula (CLNM-5′).

Each R^(NM6) independently represents a hydrogen atom, an alkyl group, acycloalkyl group, an aryl group or an atomic group represented by thefollowing Formula (CLNM-5″).

In Formula (CLNM-5), R^(NM1) is the same as R^(NM1) in Formula (CLNM-1).

In Formula (CLNM-5″), R^(NM1) is the same as R^(NM1) in Formula(CLNM-1), and R^(NM5) is the same as R^(NM3) in Formula (CLNM-5).

More specific examples of the alkyl group (preferably having 1 to 6carbon atoms), cycloalkyl group (preferably having 5 to 6 carbon atoms)and aryl group (preferably having 6 to 10 carbon atoms) of R^(NM5) andR^(NM6) include a methyl group, an ethyl group, a propyl group, anisopropyl group, a butyl group, an isobutyl group, a t-butyl group, apentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, aphenyl group, a naphthyl group and the like.

Examples of the melamine-based crosslinking agent represented by Formula(CLNM-5) include N,N,N,N,N,N-hexa(methoxymethyl)melamine,N,N,N,N,N,N-hexa(ethoxymethyl)melamine,N,N,N,N,N,N-hexa(propoxymethyl)melamine,N,N,N,N,N,N-hexa(isopropoxymethyl)melamine.N,N,N,N,N,N-hexa(butoxymethyl)melamine,N,N,N,N,N,N-hexa(t-butoxymethyl)melamine,N,N,N,N,N,N-hexa(cyclohexyloxymethyl)melamine,N,N,N,N,N,N-hexa(cyclopentyloxymethyl)melamine,N,N,N,N,N,N-hexa(adamantyloxymethyl)melamine,N,N,N,N,N,N-hexa(norbornyloxymethyl)melamine,N,N,N,N,N,N-hexa(methoxymethyl)acetoguanamine,N,N,N,N,N,N-hexa(ethoxymethyl)acetoguanamine,N,N,N,N,N,N-hexa(propoxymethyl)acetoguanamine,N,N,N,N,N,N-hexa(isopropoxymethyl)acetoguanamine,N,N,N,N,N,N-hexa(butoxymethyl)acetoguanamine,N,N,N,N,N,N-hexa(t-butoxymethyl)acetoguanamine,N,N,N,N,N,N-hexa(methoxymethyl)benzoguanamine,N,N,N,N,N,N-hexa(ethoxymethyl)benzoguanamine,N,N,N,N,N,N-hexa(propoxymethyl)benzoguanamine,N,N,N,N,N,N-hexa(isopropoxymethyl)benzoguanamine,N,N,N,N,N,N-hexa(butoxymethyl)benzoguanamine,N,N,N,N,N,N-hexa(t-butoxymethyl)benzoguanamine and the like.

The groups represented by R^(NM1) to R^(NM6) in Formulas (CLNM-1) to(CLNM-5) may further have a substituent. Examples of the substituentwhich R^(NM1) to R^(NM6) may have include a halogen atom, a hydroxylgroup, a nitro group, a cyano group, a carboxyl group, a cycloalkylgroup (preferably having 3 to 20 carbon atoms), an aryl group(preferably having 6 to 14 carbon atoms), an alkoxy group (preferablyhaving 1 to 20 carbon atoms), a cycloalkoxy group (preferably having 3to 20 carbon atoms), an acyl group (preferably having 2 to 20 carbonatoms), an acyloxy group (preferably having 2 to 20 carbon atoms) andthe like.

Hereinafter, specific examples of the compound having two or more patialstructures represented by Formula (CLNM-1) will be exemplified, but thepresent invention is not limited thereto.

(ii) The epoxy compound includes a compound represented by the followingFormula (EP 1).

In Formula (EP1), each of R^(EP1) to R^(EP3) independently represents ahydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group, andthe alkyl group and cycloalkyl group may have a substituent. Further,R^(EP1) and R^(EP2), and R_(EP2) and R_(EP3) may combine with each otherto form a ring structure.

Examples of the substituent which the alkyl group and cycloalkyl groupmay have include a hydroxyl group, a cyano group, an alkoxy group, analkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group,an alkylthio group, an alkylsulfone group, an alkylsulfonyl group, analkylamino group, an alkylamide group and the like.

Q^(EP) represents a single bond or an n^(EP)-valent organic group.R^(EF1) to R^(EP3) may combine not only with each other but also withQ^(EP) to form a ring structure.

n^(EP) represents an integer of 2 or more, and is preferably 2 to 10,and more preferably 2 to 6. However, when Q^(EP) is a single bond,n^(EP) is 2.

When Q^(EP) is an n^(EP)-valent organic group, the organic group ispreferably a chain or cyclic n^(EP)-valent saturated hydrocarbon group(preferably having 2 to 20 carbon atoms), an n^(EP)-valent aromatic ringgroup (preferably having 6 to 30 carbon atoms), or an n^(EP)-valentorganic group and the like having a structure in which a divalentlinking group such as ether, ester, amide, sulfonamide and alkylene(preferably having 1 to 4 carbon atoms, more preferably methylene), atrivalent linking group such as —N(−)₂, or a combination thereof islinked to a chain or cyclic saturated hydrocarbon or aromatichydrocarbon.

Hereinafter, specific examples of the compound having an epoxy structurewill be exemplified, but the present invention is not limited thereto.

In the present invention, the curable compound may be used either aloneor in combination of two or more thereof.

The total content of the curable compound in the coloring compositionmay vary depending on the material, but is preferably 0.1% by mass to30% by mass, more preferably 0.2% by mass to 20% by mass, andparticularly preferably 1% by mass to 10% by mass, based on the totalsolids (mass) of the coloring composition.

Meanwhile, when the curable compound is a polymer compound (that is, aresin), the solid acid number of the polymer compound is 80 mg KOH/g orless.

[4] Pigment Derivative

When the colored composition of the present invention contains a pigmentas a colorant, it is preferred to further contain a pigment derivativein order to enhance the adsorptive properties of the dispersion resin tothe pigment.

The pigment derivative refers to a compound having a structure in whicha part of an organic pigment is substituted with an acidic group, abasic group or a phthalimidemethyl group. The pigment derivativepreferably contains a pigment derivative having an acidic group or abasic group from the viewpoint of dispersibility and dispersionstability.

Examples of the organic pigments for constituting a pigment derivativeinclude diketopyrrolpyrrole-based pigments, azo-based pigments,phthalocyanine-based pigments, anthraquinone-based pigments,quinacridone-based pigments, dioxazine-based pigments, perinone-basedpigments, perylene-based pigments, thioindigo-based pigments,isoindoline-based pigments, isoindolinone-based pigments,quinophthalone-based pigments, threne-based pigments, metalcomplex-based pigments and the like.

Further, as an acidic group which the pigment derivative has, sulfonicacid, carboxylic acid and quaternary ammonium salt thereof arepreferred, a carboxylic acid group and a sulfone acid group are morepreferred, and a sulfone acid group is particularly preferred. As abasic group which the pigment derivative has, an amino group ispreferred and a tertiary amino group is preferred.

As the pigment derivative, quinoline-based, benzimidazolone-based andisoindoline-based pigment derivatives are particularly preferred andquinoline-based and benzimidazolone-based pigment derivatives are morepreferred. In particularly, a pigment derivative having the followingstructure is preferred.

A-BC-D-E_(t)  (P)

In Formula (P), A represents a partial structure selected from thefollowing Formula (PA-1) to Formula (PA-3). B represents a single bondor a (t+1)-valent linking group. C represents a single bond, —NH—,—CONH—, —CO₂—, —SO₂NH—, —O—, —S— or —SO₂—. D represents a single bond,an alkylene group, a cycloalkylene group or an arylene group. Erepresents —SO₃H, —SO₃M (M represents an alkali metal atom), —CO₂H or—N(Rpa)(Rpb). Each of Rpa and Rpb independently represents an alkylgroup, a cycloalkyl group or an aryl group, and Rpa and Rpb may combinewith each other to form a ring. t represents an integer of 1 to 5.

In Formula (PA-1) and Formula (PA-2), Rp1 represents an alkyl group oran aryl group having 1 to 5 carbon atoms. In Formula (PA-3), Rp2represents a halogen atom, an alkyl group or a hydroxyl group. srepresents an integer of 0 to 4. When s is 2 or higher, each Rp2 may bethe same as or different from every other Rp2. In Formula (PA-1) andFormula (PA-3), Rp3 represents a single bond, —NH—, —CONH—, —CO₂—,—SO₂NH—, —O—, —S— or —SO₂—. * represents a linking portion with B.

In Formula (P), Rp1 is particularly preferably a methyl group or aphenyl group and most preferably a methyl group. In Formula (PA-3), Rp2is preferably a hydrogen atom, and most preferably a chlorine atom.

In Formula (P), examples of the (t+1)-valent linking group representedby B include an alkylene group, a cycloalkylene group, an arylene groupand a hetero arylene group. Among them, a linking group represented bythe following structural formulas (PA-4) to (PA-9) is particularlypreferred.

Among the structural formulas (PA-4) to (PA-9), particularly a pigmentderivative having a linking group represented by structural formula(PA-5) or (PA-8) as B is preferred due to excellent dispersibility.

In Formula (P), examples of the alkylene group, cycloalkylene group andarylene group represented by D include methylene, ethylene, propylene,butylene, pentylene, hexylene, decylene, cyclopropylene, cyclobutylene,cyclopentylene, cyclohexylene, cyclooctylene, cyclodecylene, phenylene,naphthylene, and the like. Among them, an alkylene group is particularlypreferred as D, and alkylene having 1 to 5 carbon atoms is mostpreferred.

In Formula (P), when E represents —N(Rpa)(Rpb), examples of the alkylgroup, cycloalkyl group and aryl group in the Rpa and Rpb includemethyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl,isopentyl, neopentyl, hexyl, octyl, decyl, cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, phenyl, naphthyl andthe like. As the Rpa and Rpb, an alkyl group is particularly preferred,and an alkyl group having 1 to 5 carbon atoms is most preferred. The tis preferably 1 or 2.

Hereinafter, specific examples of the pigment derivatives will be shown,but the present invention is not limited thereto. Meanwhile, in thefollowing specific examples, M represents an alkali metal (Na, K and thelike).

Among the pigment derivatives, preferred are (A-1), (A-2), (A-5), (A-9),(A-10), (A-11), (A-19), (A-20), (A-21), (A-22), (A-23), (A-24) and(A-25), and more preferred are (A-1), (A-2), (A-9), (A-10) and (A-23).

The content of the pigment derivative in the coloring composition of thepresent invention is preferably 1% by mass to 30% by mass, and morepreferably 3% by mass to 20% by mass, based on the total mass of thepigment. Pigment derivatives may be used either alone or in combinationof two or more thereof.

[5] Acid Anhydride

The coloring composition of the present invention may contain an acidanhydride. The crosslinking properties by heat curing of a curablecompound, particularly, an epoxy compound may be improved by containingan acid anhydride.

Examples of the acid anhydride include phthalic anhydride, nadicanhydride, maleic anhydride, succinic anhydride and the like. Amongthem, phthalic anhydride is preferred in that the acid anhydride has alittle effect on pigment dispersion.

Amine-based compounds are also commonly used as an epoxy curing agent,but are advantageous in a relatively long pot life and the like.

The content of an acid anhydride in the coloring composition ispreferably 10% by mass to 40% by mass, and more preferably 15% by massto 30% by mass, based on the content of the curable compound(particularly, epoxy compound). When the content of the acid anhydrideis 10% by mass or more, the crosslinking density of a curable compound,particularly, epoxy is improved, and thus mechanical strength may beincreased. When the content is 40% by mass or less, heat curingcomponents in the coating film are suppressed, which is advantageous inincreasing the concentration of a color material.

[6] Solvent

The coloring composition of the present invention may be generallycomposed by using a solvent (usually, organic solvent). The solvent isnot basically particularly limited, as long as the solubility of eachcomponent or the coatability of the coloring curable composition issatisfied.

Examples of the organic solvent suitably include esters, for example,ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamylacetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethylbutyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyloxyacetate (for example: methyl oxyacetate, ethyl oxyacetate, butyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate,butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate and thelike)), 3-oxypropionic acid alkyl esters (for example: methyl3-oxypropionate, ethyl 3-oxypropionate and the like (for example, methyl3-methoxypropionate, ethyl 3-methoxypropionate, methyl3-ethoxypropionate, ethyl 3-ethoxypropionate and the like)),2-oxypropionic acid alkyl esters (for example: methyl 2-oxypropionate,ethyl 2-oxypropionate, propyl 2-oxypropionate and the like (for example,methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl2-methoxypropionate, methyl 2-ethoxypropionate and ethyl2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl2-oxy-2-methylpropionate (for example, methyl2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate and thelike), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methylacetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl2-oxobutanoate and the like, ethers, for example, diethylene glycoldimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether,ethylene glycol monoethyl ether, methyl cellosolve acetate, ethylcellosolve acetate, diethylene glycol monomethyl ether, diethyleneglycol monoethyl ether, diethylene glycol monobutyl ether, propyleneglycol monomethyl ether, propylene glycol monomethyl ether acetate,propylene glycol monoethyl ether acetate, propylene glycol monopropylether acetate and the like, ketones, for example, methyl ethyl ketone,cyclohexanone, 2-heptanone, 3-heptanone and the like, and aromatichydrocarbons, for example, toluene, xylene and the like.

For these solvents, a form of mixing two or more thereof is alsopreferred from the viewpoint of improving the coated surface shape andthe like. In this case, particularly preferred is a mixed solutionconsisting of two or more selected from methyl 3-ethoxypropionate, ethyl3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethyleneglycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate,2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitolacetate, propylene glycol methyl ether and propylene glycol methyl etheracetate, as described above.

From the viewpoint of coatability, the content of the solvent in thecoloring composition is preferably set such that the total solidsconcentration of the composition becomes 5% by mass to 80% by mass, morepreferably 5% by mass to 60% by mass, and particularly preferably 10% bymass to 50% by mass.

[7] Various Additives

In the coloring composition of the present invention, various additives,for example, a polymerization initiator, a polymerizable compound, asurfactant, a curing agent, a curing catalyst, a polymerizationinhibitor, a silane coupling agent, a filler, an adhesion promoter, anantioxidant, a UV absorbent, an aggregation inhibitor may be blended, ifnecessary, in a range where the effect of the present invention is notimpaired.

(Polymerization Initiator)

The coloring composition of the present invention may also contain apolymerization initiator.

As the polymerization initiator in the present invention, apolymerization initiator known as the polymerization initiators to bedescribed below may be used.

The polymerization initiator is not particularly limited as long as thepolymerization initiator has an ability to initiate the polymerizationof a polymerizable compound to be described below in detail, and may besuitably selected from known polymerization initiators. For example, apolymerization initiator having photosensitivity to visible light in theultraviolet ray region is preferred. In addition, the polymerizationinitiator may be an activator which causes any action with aphoto-excited sensitizer to produce an active radical and may be aninitiator which initiates the cationic polymerization according to thekind of the monomer.

Furthermore, it is preferred that the polymerization initiator containsat least one compound having a molecular absorption coefficient of atleast about 50 within the range of about 300 nm to 800 nm (morepreferably from 330 nm to 500 nm).

Examples of the polymerization initiator include a halogenatedhydrocarbon derivative (for example, a compound having a triazinestructure), a compound having an oxadiazole structure and the like), anacylphosphine compound such as acylphosphine oxide, hexaarylbiimidazole,an oxime compound such as oxime derivative, an organic peroxide, a thiocompound, a ketone compound, an aromatic onium salt, a ketoxime ether,an aminoacetophenone compound, hydroxyacetophenone and the like.

Examples of the halogenated hydrocarbon compound having a triazinestructure include the compounds as described in Wakabayashi et al.,Bull. Chem. Soc. Japan, 42, 2924 (1969), the compounds as described inGB Patent No. 1388492, the compounds as described in Japanese PatentApplication Laid-Open No. S53-133428, the compounds as described inGerman Patent No. 3337024, the compounds as described in F. C. Schaeferet al., J. Org. Chem.; 29, 1527 (1964), the compounds as described inJapanese Patent Application Laid-Open No. S62-58241, the compounds asdescribed in Japanese Patent Application Laid-Open No. H5-281728, thecompounds as described in Japanese Patent Application Laid-Open No.H5-34920, the compounds as described in U.S. Pat. No. 4,212,976 and thelike.

Examples of the compounds as described in U.S. Pat. No. 4,212,976include a compound having an oxadiazole structure (for example,2-trichloromethyl-5-phenyl-1,3,4-oxadiazole,2-trichloromethyl-5-(4-chlorophenyl)-1,3,4-oxadiazole,2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole,2-trichloromethyl-5-(2-naphthyl)-1,3,4-oxadiazole,2-tribromomethyl-5-phenyl-1,3,4-oxadiazole,2-tribromomethyl-5-(2-naphthyl)-1,3,4-oxadiazole;2-trichloromethyl-5-styryl-1,3,4-oxadiazole,2-trichloromethyl-5-(4-chlorostyryl)-1,3,4-oxadiazole,2-trichloromethyl-5-(4-methoxystyryl)-1,3,4-oxadiazole,2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole,2-trichloromethyl-5-(4-n-buthoxystyryl)-1,3,4-oxadiazole,2-tribromomethyl-5-styryl-1,3,4-oxadiazole and the like) and the like.

Further, examples of the polymerization initiator other than thepolymerization initiators described above include an acridine derivative(for example, 9-phenylacridine, 1,7-bis(9,9′-acridinyl)heptane and thelike), N-phenylglycine and the like, a polyhalogen compound (forexample, carbon tetrabromide, phenyl tribromomethyl sulfone, phenyltrichloromethyl ketone and the like), coumarins (for example,3-(2-benzofuranoyl)-7-diethylaminocoumarin,3-(2-benzofuroyl)-7-(1-pyrrolidinyl)coumarin,3-benzoyl-7-diethylaminocoumarin,3-(2-methoxybenzoyl)-7-diethylaminocoumarin,3-(4-dimethylaminobenzoyl)-7-diethylaminocoumarin,3,3′-carbonylbis(5,7-di-n-propoxycoumarin),3,3′-carbonylbis(7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin,3-(2-furoyl)-7-diethylaminocoumarin,3-(4-diethylaminocinnamoyl)-7-diethylaminocoumarin,7-methoxy-3-(3-pyridylcarbonyl)coumarin,3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, coumarincompounds as described in Japanese Patent Application Laid-Open Nos.H5-19475, H7-271028, 2002-363206, 2002-363207, 2002-363208 and2002-363209, and the like), acylphosphine oxides (for example,bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide,bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphenylphosphine oxide,LucirinTPO and the like), metallocenes (for example,bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium,η5-cyclopentadienyl-η6-cumenyl-iron(1+)-hexafluorophosphate (1−) and thelike), the compounds as described in Japanese Patent ApplicationLaid-Open No. S53-133428, Japanese Patent Publication Nos. S57-1819 andS57-6096 and U.S. Pat. No. 3,615,455, and the like.

Examples of the ketone compound include benzophenone,2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone,4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone,4-bromobenzophenone, 2-carboxybenzophenone,2-ethoxycarbonylbenzophenone, benzophenone tetracarboxylic acid or atetramethyl ester thereof, 4,4′-bis(dialkylamino)benzophenones (forexample, 4,4′-bis(dimethylamino)benzophenone,4,4′-bisdicyclohexylamino)benzophenone,4,4′-bis(diethylamino)benzophenone,4,4′-bis(dihydroxyethylamino)benzophenone,4-methoxy-4′-dimethylaminobenzophenone, 4,4′-dimethoxybenzophenone,4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl,anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone,phenanthraquinone, xanthone, thioxanthone, 2-chloro-thioxanthone,2,4-diethylthioxanthone, fluorenone,2-benzyl-dimethylamino-1-(4-morpholinophenyl)-1-butanone,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone,2-hydroxy-2-methyl-[4-(1-methylvinyl)phenyl]propanol oligomer, benzoin,benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether,benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether,benzyl dimethyl ketal), acridone, chloroacridone, N-methylacridone,N-butylacridone, N-butyl-chloroacridone and the like.

As the polymerization initiator, a hydroxyacetophenone compound, anaminoacetophenone compound and an acylphosphine compound may also besuitably used. More specifically, for example, anaminoacetophenone-based initiator as described in Japanese PatentApplication Laid-Open No. F110-291969 and an acylphosphine oxide-basedinitiator as described in Japanese Patent No. 4225898 may also be used.

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173,IRGACURE-500, IRGACURE-2959 and IRGACURE-127 (trade names: allmanufactured by BASF Corp.) may be used. As the aminoacetophenone-basedinitiator, commercially available products IRGACURE-907, IRGACURE-369and IRGACURE-379 (trade names: all manufactured by BASF Corp.) may beused. As the aminoacetophenone-based initiator, the compounds asdescribed in Japanese Patent Application Laid-Open No. 2009-191179,where the absorption wavelength matches the light source having a longwavelength such as 365 nm or 405 nm, may also be used. In addition, asthe acylphosphine-based initiator, commercially available productsIRGACURE-819 or DAROCUR-TPO (trade names: all manufactured by BASFCorp.) may be used.

The polymerization initiator more preferably includes an oxime-basedcompound. As specific examples of the oxime-based initiator, thecompounds as described in Japanese Patent Application Laid-Open No.2001-233842, the compounds as describe in Japanese Patent ApplicationLaid-Open No. 2000-80068 and the compounds as described in JapanesePatent Application Laid-Open No. 2006-342166 may be used.

Examples of the oxime compound such as oxime derivative, which issuitably used as the polymerization initiator in the present invention,include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one,3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one,2-acetoxyimino-1-phenylpropan-1-one,2-benzoyloxyimino-1-phenylpropan-1-one,3-(4-toluenesulfonyloxy)iminobutan-2-one,2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

Examples of the oxime compounds include the compounds as described in J.C. S. Perkin II (1979) pp. 1653-1660, J. C. S. Perkin II (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995) pp202-232, Japanese Patent Application Laid-Open Nos. 2000-66385 and2000-80068, Japanese Patent Application Laid-Open No. 2004-534797,Japanese Patent Application Laid-Open No. 2006-342166, and the like.

As the commercially available product, IRGACURE-OXE01 (manufactured byBASF Corp.) and IRGACURE-OXE02 (manufactured by BASF Corp.) may also besuitably used.

In addition, as the oxime compound other than oxime compounds describedabove, the compounds as described in Japanese Patent ApplicationLaid-Open No. 2009-519904, where oxime is linked to the N-position ofcarbazole, the compounds as described in U.S. Pat. No. 7,626,957, wherea hetero-substituent is introduced into the benzophenone moiety, thecompounds as described in Japanese Patent Application Laid-Open No.2010-15025 and U.S. Patent Application Publication No. 2009-292039,where a nitro group is introduced into the dye moiety, theketoxime-based compounds as described in International Publication No.2009-131189, the compounds as described in U.S. Pat. No. 7,556,910,containing a triazine structure and an oxime structure within the samemolecule, the compounds as described in Japanese Patent ApplicationLaid-Open No. 2009-221114, having an absorption maximum at 405 nm andexhibiting good sensitivity for a g-ray light source, and the like mayalso be used.

Preferably, furthermore, cyclic oxime compounds as described in JapanesePatent Application Laid-Open No. 2007-231000 and Japanese PatentApplication Laid-Open No. 2007-322744 may also be suitably used. Amongcyclic oxime compounds, the cyclic oxime compounds condensed to acarbazole dye, as described in Japanese Patent Application Laid-Open No.2010-32985 and Japanese Patent Application Laid-Open No. 2010-185072,have high light absorptivity and thus are particularly preferred fromthe viewpoint of high sensitivity.

Further, in the compounds as described in Japanese Patent ApplicationLaid-Open No. 2009-242469, having an unsaturated bond at a specific siteof an oxime compound, high sensitivity may also be achieved byregenerating an active radical from a polymerization inactive radical,and thus the compounds may be suitably used.

Most preferred is the oxime compound having a specific substituent asdescribed in Japanese Patent Application Laid-Open No. 2007-269779 orthe oxime compound having a thioaryl group as described in JapanesePatent Application Laid-Open No. 2009-191061.

Specifically, the oxime-based polymerization initiator compound ispreferably a compound represented by the following formula (OX-1). Inaddition, the N—O bond of the oxime bond may be an oxime compound of (E)form, an oxime compound of (Z) form, or a mixture of (E) form and (Z)form.

(in Formula (OX-1), each of R and B independently represents amonovalent substituent, A represents a divalent organic group, and Arrepresents an aryl group).

In Formula (OX-1), the monovalent substituent represented by R ispreferably a monovalent nonmetallic atom group.

Examples of the monovalent nonmetallic atom group include an alkylgroup, an aryl group, an acyl group, an alkoxycarbonyl group, anaryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group,an arylthiocarbonyl group and the like. Further, these groups may haveone or more substituents. In addition, the above-described substituentmay be substituted with another substituent.

Examples of the substituent include a halogen atom, an aryloxy group, analkoxycarbonyl group, or an aryloxycarbonyl group, an acyloxy group, anacyl group, an alkyl group, an aryl group and the like.

As the alkyl group which may have a substituent, an alkyl group having 1to 30 carbon atoms is preferred, and specific examples thereof include amethyl group, an ethyl group, a propyl group, a butyl group, a hexylgroup, an octyl group, a decyl group, a dodecyl group, an octadecylgroup, an isopropyl group, an isobutyl group, a sec-butyl group, at-butyl group, a 1-ethylpentyl group, a cyclopentyl group, a cyclohexylgroup, a trifluoromethyl group, a 2-ethylhexyl group, a phenacyl group,a 1-naphthoylmethyl group, a 2-naphthoylmethyl group, a4-methylsulfanylphenacyl group, a 4-phenylsulfanylphenacyl group, a4-dimethylaminophenacyl group, a 4-cyanophenacyl group, a4-methylphenacyl group, a 2-methylphenacyl group, a 3-fluorophenacylgroup, a 3-trifluoromethylphenacyl group and a 3-nitrophenacyl group.

As the aryl group which may have a substituent, an aryl group having 6to 30 carbon atoms is preferred, and specific examples thereof include aphenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group,a 9-anthryl group, a 9-phenanthryl group, a 1-pyrenyl group, a5-naphthacenyl group, a 1-indenyl group, a 2-azulenyl group, a9-fluorenyl group, a terphenyl group, a quarter phenyl group, an o-tolylgroup, a m-tolyl group, p-tolyl group, a xylyl group, an o-cumenylgroup, a m-cumenyl group, a p-cumenyl group, a mesityl group, apentalenyl group, a binaphthalenyl group, a ternaphthalenyl group, aquarter naththalenyl group, a heptalenyl group, a biphenylenyl group, anindacenyl group, a fluoranthenyl group, an acenaphthylenyl group, anaceanthrylenyl group, a phenalenyl group, a fluorenyl group, an anthrylgroup, a bianthracenyl group, a teranthracenyl group, a quarteranthracenyl group, an anthraquinolyl group, a phenanthryl group, atriphenylenyl group, a pyrenyl group, a chrysenyl group, a naphthacenylgroup, a pleiadenyl group, a picenyl group, a perylenyl group, apentaphenyl group, a pentacenyl group, a tetraphenylenyl group, ahexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenylgroup, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group,a pyranthrenyl group and an ovalenyl group.

As the acyl group which may have a substituent, an acyl group having 2to 20 carbon atoms is preferred, and specific examples thereof includean acetyl group, a propanoyl group, a butanoyl group, a trifluoroacetylgroup, a pentanoyl group, a benzoyl group, a 1-naphthoyl group, a2-naphthoyl group, a 4-methylsulfanylbenzoyl group, a4-phenylsulfanylbenzoyl group, a 4-dimethylaminobenzoyl group, a4-diethylaminobenzoyl group, a 2-chlorobenzoyl group, a 2-methylbenzoylgroup, a 2-methoxybenzoyl group, a 2-butoxybenzoyl group, a3-chlorobenzoyl group, a 3-trifluoromethylbenzoyl group, a3-cyanobenzoyl group, a 3-nitrobenzoyl group, a 4-fluorobenzoyl group, a4-cyanobenzoyl group and a 4-methoxybenzoyl group.

As the alkoxycarbonyl group which may have a substituent, analkoxycarbonyl group having 2 to 20 carbon atoms is preferred, andspecific examples thereof include a methoxycarbonyl group, anethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, ahexyloxycarbonyl group, an octyloxycarbonyl group, a decyloxycarbonylgroup, an octadecyloxycarbonyl group and a trifluoromethyloxycarbonylgroup.

Specific examples of the aryloxycarbonyl group which may have asubstituent include a phenoxycarbonyl group, a 1-naphthyloxycarbonylgroup, a 2-naphthyloxycarbonyl group, a4-methylsulfanylphenyloxycarbonyl group, a4-phenylsulfanylphenyloxycarbonyl group, a4-dimethylaminophenyloxycarbonyl group, a4-diethylaminophenyloxycarbonyl group, a 2-chlorophenyloxycarbonylgroup, a 2-methylphenyloxycarbonyl group, a 2-methoxyphenyloxycarbonylgroup, a 2-butoxyphenyloxycarbonyl group, a 3-chlorophenyloxycarbonylgroup, a 3-trifluoromethylphenyloxycarbonyl group, a3-cyanophenyloxycarbonyl group, a 3-nitrophenyloxycarbonyl group, a4-fluorophenyloxycarbonyl group, a 4-cyanophenyloxycarbonyl group and a4-methoxyphenyloxycarbonyl group.

As the heterocyclic group which may have a substituent, an aromatic oraliphatic heterocycle including a nitrogen atom, an oxygen atom, asulfur atom or a phosphorus atom is preferred.

Specific examples thereof include a thienyl group, a benzo[b]thienylgroup, a naphtho[2,3-b]thienyl group, a thianthrenyl group, a furylgroup, a pyranyl group, an isobenzofuranyl group, a chromenyl group, axanthenyl group, a phenoxathiinyl group, a 2H-pyrrolyl group, a pyrrolylgroup, an imidazolyl group, a pyrazolyl group, a pyridyl group, apyrazinyl group, a pyrimidinyl group, a pyridazinyl group, anindolizinyl group, an isoindolyl group, a 3H-indolyl group, an indolylgroup, a 1H-indazolyl group, a purinyl group, a 4H-quinolizinyl group,an isoquinolyl group, a quinolyl group, a phthalazinyl group, anaphthyridinyl group, a quinoxalinyl group, a quinazolinyl group, acinnolinyl group, a pteridinyl group, a 4aH-carbazolyl group, acarbazolyl group, a 13-carbolinyl group, a phenanthridinyl group, anacridinyl group, a perimidinyl group, a phenanthrolinyl group, aphenazinyl group, a phenarsazinyl group, an isothiazolyl group, aphenothiazinyl group, an isoxazolyl group, a furazanyl group, aphenoxazinyl group, an isochromanyl group, a chromanyl group, apyrrolidinyl group, a pyrrolinyl group, an imidazolidinyl group, animidazolinyl group, a pyrazolidinyl group, a pyrazolinyl group, apiperidyl group, a piperazinyl group, an indolinyl group, anisoindolinyl group, a quinuclidinyl group, a morpholinyl group and athioxantholyl group.

Specific examples of the alkylthiocarbonyl group which may have asubstituent include a methylthiocarbonyl group, a propylthiocarbonylgroup, a butylthiocarbonyl group, a hexylthiocarbonyl group, anoctylthiocarbonyl group, a decylthiocarbonyl group, anoctadecylthiocarbonyl group and a trifluoromethyl thiocarbonyl group.

Specific examples of the arylthiocarbonyl group which may have asubstituent include a 1-naphthylthiocarbonyl group, a2-naphthylthiocarbonyl group, a 4-methylsulfanylphenylthiocarbonylgroup, a 4-phenylsulfanylphenylthiocarbonyl group, a4-dimethylaminophenylthiocarbonyl group, a4-diethylaminophenylthiocarbonyl group, a 2-chlorophenylthiocarbonylgroup, a 2-methylphenylthiocarbonyl group, a 2-methoxyphenylthiocarbonylgroup, a 2-butoxyphenylthiocarbonyl group, a 3-chlorophenylthiocarbonylgroup, a 3-trifluoromethylphenylthiocarbonyl group, a3-cyanophenylthiocarbonyl group, a 3-nitrophenylthiocarbonyl group, a4-fluorophenylthiocarbonyl group, a 4-cyanophenylthiocarbonyl group anda 4-methoxyphenylthiocarbonyl group.

In the Formula (OX-1), the monovalent substituent represented by Brepresents an aryl group, a heterocyclic group, an arylcarbonyl group ora heterocyclic carbonyl group. In addition, these groups may have one ormore substituents. As the substituent, the above-described substituentsmay be exemplified. Further, the above-described substituent may besubstituted with another substituent.

Among them, structures shown below are particularly preferred.

In the structures, Y, X and n have the same meanings as Y, X and n inFormula (OX-2) described below, and preferred examples thereof are alsothe same.

In the Formula (OX-1), examples of the divalent organic grouprepresented by A include an alkylene group having 1 to 12 carbon atoms,a cycloalkylene group having 6 to 12 carbon atoms and an alkynylenegroup having 2 to 12 carbon atoms. Further, these groups may have one ormore substituents. As the substituent, the above-described substituentsmay be exemplified. In addition, the above-described substituent may besubstituted with another substituent.

Among them, from the viewpoint of increasing the sensitivity to suppressthe coloration as the heating time passes, A in Formula (OX-1) ispreferably an unsubstituted alkylene group, an alkylene groupsubstituted with an alkyl group (for example, a methyl group, an ethylgroup, a tert-butyl group and a dodecyl group), an alkylene groupsubstituted with an alkenyl group (for example, a vinyl group and anallyl group), and an alkylene group substituted with an aryl group (forexample, a phenyl group, a p-tolyl group, a xylyl group, a cumenylgroup, a naphthyl group, an anthryl group, a phenanthryl group and astyryl group).

In Formula (OX-1), the aryl group represented by Ar is preferably anaryl group having from 6 to 30 carbon atoms, and may have a substituent.As the substituent, the substituents introduced into the substitutedaryl group exemplified above as a specific example of the aryl groupwhich may have a substituent may be exemplified.

Among them, from the viewpoint of increasing the sensitivity to suppressthe coloration as the heating time passes, a substituted orunsubstituted phenyl group is preferred.

in Formula (OX-1), from the viewpoint of the sensitivity, the structureof “SAr” formed by Ar in Formula (OX-1) and S adjacent thereto ispreferably the structure shown below. Further, Me represents a methylgroup, and Et represents an ethyl group.

The oxime compound is preferably a compound represented by the followingformula (OX-2).

(In Formula (OX-2), each of R and X independently represents amonovalent substituent, each of A and Y independently represents adivalent organic group, Ar represents an aryl group, and n is an integerof 0 to 5.)

In Formula (OX-2), R, A and Ar have the same meanings as R, A and Ar inFormula (OX-1), and preferred examples thereof are also the same.

In Formula (OX-2), examples of the monovalent substituent represented byX include an alkyl group, an aryl group, an alkoxy group, an aryloxygroup, an acyloxy group, an acyl group, an alkoxycarbonyl group, anamino group, a heterocyclic group, and a halogen atom. Further, thesegroups may have one or more substituents. As the substituent, theabove-described substituents may be exemplified. Further, theabove-described substituent may be substituted with another substituent.

Among them, from the viewpoint of solvent solubility and enhancement ofabsorption efficiency in the long wavelength region, X in Formula (OX-2)is preferably an alkyl group.

In addition, In Formula (OX-2), n represents an integer of 0 to 5, andpreferably an integer of 0 to 2.

In Formula (OX-2), examples of the divalent organic group represented byY include structures shown below. Meanwhile, in the groups shown below,“*” represents a bonding position to the carbon atom adjacent to Y inFormula (OX-2).

Among them, from the viewpoint of high sensitivity, structures shownbelow are preferred.

Further, the oxime compound is preferably a compound represented by thefollowing formula (OX-3).

(In Formula (OX-3), each of R and X independently represents amonovalent substituent, A represents a divalent organic group, Arrepresents an aryl group, and n is an integer of from 0 to 5.)

In Formula (OX-3), R, X, A, Ar and n have the same meanings as R, X, A,Ar and n in Formula (OX-2), and preferred examples thereof are also thesame.

Hereinafter, specific examples (B-1) to (B-10) of oxime compounds whichare suitably used will be shown, but the present invention is notlimited thereto.

The oxime compound has a maximum absorption wavelength in the wavelengthregion of 350 nm to 500 nm, preferably an absorption wavelength in thewavelength region of 360 nm to 480 nm and particularly preferably a highabsorbance of 365 nm to 455 nm.

The oxime compound has a molar absorption coefficient of preferably1,000 to 300,000, more preferably 2,000 to 300,000, and particularlypreferably 5,000 to 200,000 in 365 nm or 405 nm, from the viewpoint ofsensitivity.

The molar absorption coefficient of the compound may be measured byusing a known method, but specifically, it is preferred that thecoefficient is measured, for example, by an ultraviolet and visiblespectrophotometer (Carry-5 spectrophotometer, manufactured by VarianInc.) at a concentration of 0.01 g/L using an ethyl acetate solvent.

As the polymerization initiator used in the present invention, two ormore thereof may be used in combination, if necessary.

From the viewpoint of exposure sensitivity, the polymerization initiatorused in the coloring composition of the present invention is preferablya compound selected from the group consisting of a trihalomethyltriazine compound, a benzyl dimethyl ketal compound, an α-hydroxyketonecompound, an α-aminoketone compound, an acyl phosphine compound, aphosphine oxide compound, a metallocene compound, an oxime compound, atriallylimidazole dimer, an onium compound, a benzothiazole compound, abenzophenone compound, an acetophenone compound and the derivativesthereof, a cyclopentadiene-benzene-iron complex and the salts thereof, ahalomethyl oxadiazole compound and a 3-aryl-substituted coumarincompound.

A trihalomethyl triazine compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, an oxime compound, atriallyl imidazole dimer, an onium compound, a benzophenone compound andan acetophenone compound are more preferred, and at least one compoundselected from the group consisting of a trihalomethyl triazine compound,an α-aminoketone compound, an oxime compound, a triallyl imidazoledimer, and a benzophenone compound is most preferred.

The content of the polymerization initiator contained in the coloringcomposition of the present invention (total content in the case of twoor more kinds) is preferably 0.1% by mass to 50% by mass, morepreferably 0.5% by mass to 30% by mass, and still more preferably 1% bymass to 20% by mass, based on the total solids of the coloringcomposition.

(Polymerizable Compound)

Specifically, the polymerizable compound is selected from compoundshaving at least one terminal ethylenically unsaturated bond andpreferably two or more terminal ethylenically unsaturated bonds. Thegroup of these compounds is widely known in the relevant industrialfield, and such compounds may be used in the present invention withoutparticular limitations. These compounds may be any of chemical formssuch as, for example, a monomer, a prepolymer, that is, a dimer, atrimer, and an oligomer, or a mixture thereof, and a multimer thereof.The polymerizable compounds in the present invention may be either aloneor in combination of two or more thereof.

More specifically, examples of monomers and prepolymers thereof includean unsaturated carboxylic acid (for example, acrylic acid, methacrylicacid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid andthe like), esters and amides thereof and multimers thereof, and estersof an unsaturated carboxylic acid and an aliphatic polyhydric alcoholcompound, amides of an unsaturated carboxylic acid and an aliphaticpolyvalent amine compound, and multimers thereof. Further, an additionreaction product of unsaturated carboxylic acid esters or unsaturatedcarboxylic acid amides, which have a nucleophilic substituent such as ahydroxyl group, an amino group and a mercapto group, with monofunctionalor polyfunctional isocyanates or epoxies, a dehydration condensationreaction product of the unsaturated carboxylic acid esters orunsaturated carboxylic acid amides with a monofunctional orpolyfunctional carboxylic acid, and the like are also suitably used. Inaddition, an addition reaction product of unsaturated carboxylic acidesters or unsaturated carboxylic acid amides, which have anelectrophilic substituent such as an isocyanate group and an epoxygroup, with monofunctional or polyfunctional alcohols, amines or thiols;and furthermore, a substitution reaction product of unsaturatedcarboxylic acid esters or unsaturated carboxylic acid amides, which havea releasable substituent such as a halogen group and a tosyloxy group;with monofunctional or polyfunctional alcohols, amines or thiols, arealso suitably used. Furthermore, as another example, it is also possibleto use the group of compounds obtained by replacing the above-describedunsaturated carboxylic acid with a vinyl benzene derivative such as anunsaturated phosphonic acid and styrene, vinyl ether, allyl ether andthe like.

As the specific compounds thereof, the compounds as described inparagraph Nos. [0095] to [0108] of Japanese Patent Application Laid-OpenNo. 2009-288705 may be suitably used even in the present invention.

Further, as the polymerizable compound, a compound having anethylenically unsaturated group with a boiling temperature of 100° C. ormore under normal pressure, which has at least one additionpolymerizable ethylene group, is also preferred. Examples thereofinclude monofunctional acrylates or methacrylates such as polyethyleneglycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate,phenoxyethyl(meth)acrylate and the like; compounds obtained by addingethylene oxide or propylene oxide to polyfunctional alcohols such aspolyethylene glycol di(meth)acrylate, trimethylolethanetri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritoltri(meth)acrylate, pentaerytritol tetra(meth)acrylate, dipentaerythritolpenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol(meth)acrylate, trimethylolpropane tri(acryloyloxyethyl)ether,tri(acryloyloxyethyl) isocyanurate, glycerine or trimethylolethane,followed by (meth)acrylation, urethane (meth)acrylates as described inJapanese Patent Publication Nos. S48-41708 and S50-6034 and JapanesePatent Application Laid-Open No. 51-37193, polyester acrylates asdescribed in Japanese Patent Application Laid-Open No. S48-64183 andJapanese Patent Publication Nos. S49-43191 and S52-30490,polyfunctionalacrylates or methacrylates such as epoxy acrylates as areaction product obtained by reacting epoxy resins with (meth)acrylicacid, and mixtures thereof.

Examples thereof include polyfunctional (meth)acrylates obtained byreacting a cyclic ether group such as glycidyl (meth)acrylate with acompound having an ethylenically unsaturated group in a polyfunctionalcarboxylic acid, and the like.

In addition, as the other preferred polymerizable compound, it is alsopossible to use a compound having a fluorene ring and having two or moreethylenically unsaturated functional groups, as described in JapanesePatent Application Laid-Open Nos. 2010-160418 and 2010-129825 and JapanPatent No. 4364216, and cardo resins.

Furthermore, as the compound having at least one ethylenicallyunsaturated group, which is addition polymerizable, and having a boilingpoint of 100° C. or more under normal pressure, the compounds asdescribed in paragraph Nos. [0254] to [0257] of Japanese PatentApplication Laid Open No. 2008-292970 are also suitable.

In addition to the compounds described above, radical polymerizablemonomers represented by the following Formulas (MO-1) to (MO-5) may alsobe suitably used. Meanwhile, in the formulas, when T is an oxyalkylenegroup, R is bonded to the terminal end of the carbon atom side thereof.

In the Formulas, n is 0 to 14, and m is 1 to 8. Each of R and T that arepresent in plurality in a molecule may be the same as or different fromevery other R and T.

In each of the polymerizable monomers represented by Formulas (MO-1) to(MO-5), at least one of a plurality of R's represents a grouprepresented by —OC(═O)CH═CH₂ or —OC(═O)C(CH₃)═CH₂.

As specific examples of the polymerizable compounds represented byFormulas (MO-1) to (MO-5), the compounds as disclosed in paragraph Nos.[0248] to [0251] of Japanese Patent Application Laid-Open No.2007-269779 may be suitably used even in the present invention.

Further, the compounds, described as a compound of Formula (1) and (2)together with specific examples thereof in Japanese Patent ApplicationLaid-Open No. H10-62986, which are obtained by adding ethylene oxide orpropylene oxide to the polyfunctional alcohol followed by(meth)acrylation may be also used as the polymerizable compound.

Among them, dipentaerythritol triacrylate (as a commercially availableproduct thereof, KAYARAD D-330; manufactured by NIPPON KAYAKU Co.,Ltd.), dipentaerythritol tetraacrylate (as a commercially availableproduct thereof, KAYARAD D-320; manufactured by NIPPON KAYAKU Co.,Ltd.), dipentaerythritol penta(meth)acrylate (as a commerciallyavailable product thereof, KAYARAD D-310; manufactured by NIPPON KAYAKUCo., Ltd.), dipentaerythritol hexa(meth)acrylate (as a commerciallyavailable product thereof, KAYARAD DPHA; manufactured by NIPPON KAYAKUCo., Ltd.), polyfunctional acrylate (as a commercially available productthereof, KAYARAD RP-1040; manufactured by NIPPON KAYAKU Co., Ltd.) and astructure in which the (meth)acryloyl group thereof has an ethyleneglycol or propylene glycol reside therethrough are preferred as thepolymerizable compound. The oligomer types thereof may also be used.Hereinafter, aspects of preferred polymerizable compounds will be shown.

The polymerizable compound is a polyfunctional monomer, and may have anacid group such as a carboxyl group, a sulfonic acid group and aphosphoric acid group. The ethylenic compound may be used as it is aslong as the ethylenic compound has an unreacted carboxyl group, but ifnecessary, an acid group may be introduced by reacting a non-aromaticcarboxylic anhydride with a hydroxyl group of the above-describedethylenic compound. In this case, specific examples of the non-aromaticcarboxylic anhydride to be used include tetrahydrophthalic anhydride,alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride,alkylated hexahydrophthalic anhydride, succinic anhydride and maleicanhydride.

In the present invention, a monomer having an acid group is an ester ofan aliphatic polyhydroxy compound with an unsaturated carboxylic acidand is preferably a polyfunctional monomer which is allowed to have anacid group by reacting a non-aromatic carboxylic anhydride with anunreacted hydroxyl group of an aliphatic polyhydroxy compound, and thealiphatic polyhydroxy compound is particularly preferablypentaerythritol and/or dipentaerythritol in the ester. Examples of thecommercially available product include polybasic acid modified-acrylicoligomers manufactured by TOAGOSEI CO., LTD., such as M-510 and M-520.

These monomers may be used alone, but may be used in mixture of two ormore thereof because it is difficult to use a single compound in thepreparation. Further, if necessary, a polyfunctional monomer which hasno acid group as a monomer may be used in combination with apolyfunctional monomer which has an acid group.

The polyfunctional monomer which has an acid group preferably has anacid number of 0.1 to 40 mg KOH/g, and particularly preferably 5 to 30mg KOH/g. When the polyfunctional monomers having another acid group areused in combination of two or more thereof, or the polyfunctionalmonomers which have no acid group are used in combination, it ispreferred to adjust the acid number such that the acid group as thetotal polyfunctional monomer falls within the above-described range.

In addition, it is a preferred aspect that a polyfunctional monomerhaving a caprolactone structure is also contained as a polymerizablemonomer.

The polyfunctional monomer having a caprolactone structure is notparticularly limited as long as the monomer has a caprolactone structurein the molecule thereof, but, for example, is obtained by esterificationof a polyhydric alcohol such as trimethylolethane, ditrimethylolethane,trimethylolpropane, ditrimethylolpropane, pentaerythritol,dipentaerythritol, tripentaerythritol, glycerine, diglycerol,trimethylolmelamine and the like, (meth)acrylic acid and ε-caprolactone,and examples thereof include ε-caprolactone modified polyfunctional(meth)acrylates. Among them, a polyfunctional monomer having acaprolactone structure represented by the following Formula (Z-1) ispreferred.

In Formula (Z-1), all of six R's are a group represented by thefollowing Formula (Z-2), or 1 to 5 of six R's are a group represented bythe following Formula (Z-2) and the remainder thereof is a grouprepresented by the following Formula (Z-3).

In Formula (Z-2), R¹ represents a hydrogen atom or a methyl group, mrepresents a number of 1 or 2, and “*” represents a bonding hand.

In Formula (Z-3), R¹ represents a hydrogen atom or a methyl group, and“*” represents a bonding hand.)

The polyfunctional monomer having such a caprolactone structure iscommercially available, for example, as KAYARAD DPCA series from NIPPONKAYAKU Co., Ltd., and examples thereof include DPCA-20 (in Formulas(Z-1) to (Z-3), a compound in which m=1, the number of groupsrepresented by Formula (Z-2)=2, and all of R¹ are a hydrogen atom),DPCA-30 (in the same formulas, a compound in which m=1, the number ofgroups represented by Formula (Z-2)=3, and all of R¹ are a hydrogenatom), DPCA-60 (in the same formulas, a compound in which m=1, thenumber of groups represented by Formula (Z-2)=6, and all of R¹ are ahydrogen atom), DPCA-120 (in the same formula, a compound in which m=2,the number of groups represented by Formula (Z-2)=6, and all of R¹ are ahydrogen atom) and the like.

In the present invention, a polyfunctional monomer having a caprolactonestructure may be used either alone or in combination of two or morethereof.

Further, as the curable compound in the present invention, at least oneselected from the group of the compound represented by the followingFormula (Z-4) or Formula (Z-5) is also preferred.

In Formula (Z-4) and Formula (Z-5), each of E independently represents—((CH₂)_(y)CH₂O)— or —((CH₂)_(y)CH(CH₃)O)—, each of y independentlyrepresents an integer of 0 to 10, each of X independently represents anacryloyl group, a methacryloyl group, a hydrogen atom or a carboxylgroup.

In Formula (Z-4), the sum of an acryloyl group and a methacryloyl groupis 3 or 4, each of m independently represents an integer of 0 to 10, andthe sum of each m is an integer of 0 to 40. However, when the sum ofeach m is 0, any one of X is a carboxyl group.

In Formula (Z-5), the sum of an acryloyl group and a methacryloyl groupis 5 or 6, each of n independently represents an integer of 0 to 10, andthe sum of each n is an integer of 0 to 60. However, when the sum ofeach n is 0, any one of X is a carboxyl group.

In Formula (Z-4), m is preferably an integer of 0 to 6, and morepreferably an integer of 0 to 4.

Further, the sum of each m is preferably an integer of 2 to 40, morepreferably an integer of 2 to 16, and particularly preferably an integerof 4 to 8.

In Formula (Z-5), n is preferably an integer of 0 to 6, and morepreferably an integer of 0 to 4.

In addition, the sum of each n is preferably an integer of 3 to 60, morepreferably an integer of 3 to 24, and particularly preferably an integerof 6 to 12.

Furthermore, —((CH₂)_(y)CH₂O)— or —((CH₂)_(y)CH(CH₃)O)— in Formula (Z-4)or Formula (Z-5) is preferably a form in which X is bonded to theterminal end of the oxygen atom side.

The compound represented by Formula (Z-4) or Formula (Z-5) may be usedeither alone or in combination of two or more thereof. In particular, inFormula (Z-5), a form in which all of the six X's are an acrylolyl groupis preferred.

In addition, the total content of the compound represented by Formula(Z-4) or Formula (Z-5) in the polymerizable compound is preferably 20%by mass or more, and more preferably 50% by mass or more.

The compound represented by Formula (Z-4) or Formula (Z-5) may besynthesized by a process of bonding a ring-opening structure of ethyleneoxide or propylene oxide to pentaerythritol or dipentaerythritol bymeans of a ring-opening addition reaction and a process of reacting, forexample, (meth)acryloylchloride with a terminal hydroxyl group of thering-opening structure to introduce a (meth)acryloyl group, which areprocesses known in the related art. Each process is a well knownprocess, and the compound represented by Formula (i) or Formula (ii) maybe readily synthesized by those skilled in the art.

Even among the compositions represented by Formula (Z-4) or Formula(Z-5), pentaerythrol deritives and dipentaerythritol derivatives aremore preferred.

Specifically, examples thereof include compounds (hereinafter, alsoreferred to as “exemplary compounds (a) to (f)”) represented by thefollowing formulas (a) to (f) and among them, exemplary compounds (a),(b), (e) and (f) are preferred.

Examples of the commercially available product of the polymerizablecompounds represented by Formula (Z-4) and Formula (Z-5) include atetrafunctional acrylate having four ethyleneoxy chains, SR-494,manufactured by Sartomer Company, Inc., and a hexafunctional acrylatehaving six pentyleneoxy chains, DPCA-60 and a trifunctional acrylatehaving three isobutyleneoxy chains, TPA-330, which are both manufacturedby Nippon Kayaku Co., Ltd.

Further, as a polymerizable compound, urethane acrylates as described inJapanese Patent Publication Nos. S48-41708, S51-37193, H2-32293 andH2-16765, or urethane compounds having an ethyleneoxide-based structure,as described in Japanese Patent Publication Nos. S58-49860, S56-17654,S62-39417 and S62-39418 are also suitable. Further, a curablecomposition having excellent photosensitive speed may be obtained byusing addition polymerizable compounds having an amino structure or asulfide structure in a molecule, as described in Japanese PatentApplication Laid-Open Publication Nos. 563-277653, S63-260909, andH1-105238, as a polymerizable compound.

Examples of the commercially available product of the polymerizablecompound include urethane oligomers UAS-10, UAB-140 (manufactured bySanyo-Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by SHIN-NAKAMURACHEMICAL CO., LTD.) DPHA-40H (manufactured by NIPPON KAYAKU Co., Ltd.),UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured byKYOEISHA CHEMICAL CO., LTD.), and the like.

For these polymerizable compounds, details of the methods of usethereof, such as the structure of the compounds, single use or use of acombination and the amount to be added, may be arbitrarily determined inaccordance with the final performance design of the coloringcomposition. For example, from the viewpoint of sensitivity, a structurehaving a high content of unsaturated groups per one molecule ispreferred, and in many cases, bifunctional or higher functionality ispreferred. Further, from the viewpoint of increasing the strength of thecolored cured film, a trifunctional or higher functionality is suitable,a tetrafunctional or higher functionality is preferred, andpentafunctional or higher functionality is preferred. In addition, amethod of controlling both the sensitivity and the strength by using incombination compounds which are different in functional number anddifferent in polymerizable group (for example, an acrylic acid ester, amethacrylic acid ester, a styrene-based compound and a vinyl ether-basedcompound), is also effective. Furthermore, it is preferred to use incombination trifunctional or higher polymerizable compounds which aredifferent in ethylene oxide chain length.

Further, the selection and the method of use of the polymerizablecompounds are also important factors for compatibility with othercomponents (for example, a photopolymerization initiator, a colorant(pigment), a binder polymer and the like) contained in the coloringcomposition and for dispersibility, and for example, the compatibilitymay be increased by the use of a compound with low purity, or by thecombination use of two or more of other components in some cases. Inaddition, in some cases, a specific structure may be selected from theviewpoint of improving the adhesion to a hard surface such as a support.

The content of the polymerizable compound in the coloring composition ofthe present invention is preferably 0.1% by mass to 90% by mass, morepreferably 1.0% by mass to 80% by mass, and particularly preferably 2.0%by mass to 70% by mass, based on the solid content in the coloringcomposition.

(Surfactant)

Various surfactants may be added to the coloring composition of thepresent invention from the viewpoint of further improving thecoatability thereof. Various surfactants such as fluorine-basedsurfactants, nonionic surfactants, cationic surfactants, anionicsurfactants and silicone-based surfactants may be used as thesurfactant.

In particular, the coloring composition of the present inventioncontains a fluorine-based surfactant, and thus when the composition isprepared into a coating solution, liquid characteristics (particularly,fluidity) may be further improved, thus resulting in furtherimprovements in uniformity of a coating thickness or saving of liquid.

That is, when a film is formed by using a coating solution in which acoloring composition containing a fluorine-based surfactant is coated,wettability into a surface to be coated is improved by reducing theinterfacial tension between the surface to be coated and the coatingsolution, thereby improving the coatability into the surface to becoated. For this reason, it is effective in that the formation of auniform-thickness film with a slight thickness unevenness may be moresuitably carried out, even when a thin film of approximately several μmis formed with a small amount of the liquid.

The fluorine content by percentage in the fluorine-based surfactant issuitably 3% by mass to 40% by mass, more preferably 5% by mass to 30% bymass, and particularly preferably 7% by mass to 25% by mass. Thefluorine-based surfactant having a fluorine content, which falls withinthe this range, is effective from the viewpoint of thickness uniformityof the coating film and saving of liquid, and also exhibits goodsolubility in the coloring composition.

Examples of the fluorine-based surfactant include MEGAFACE F781(manufactured by DIC Corporation) and the like.

The surfactants may be used either alone or in combination of two ormore thereof.

The coloring composition may or may not contain a surfactant, but whenthe composition contains a surfactant, the amount of the surfactantadded is preferably 0.001% by mass to 2.0% by mass, and more preferably0.005% by mass to 1.0% by mass, based on the total mass of the coloringcomposition.

Meanwhile, when the surfactant is a polymer compound (that is, a resin),the solid acid number of the polymer compound is 80 mg KOH/g or less.

(Curing Agent)

When an epoxy resin is used as a curable compound, a curing agent ispreferably added. A curing agent for an epoxy resin has a very widevariety, and property, a working life for a mixture of the resin and thecuring agent, viscosity, a curing temperature, a curing time, heatgeneration and the like vary so greatly according to the kind of thecuring agent to be used, and thus it is required to select anappropriate curing agent depending on application purpose, serviceconditions, working conditions of the curing agent and the like. Thecuring agent is explained in detail in “Epoxy Resin (SHOKODO)” edited byKakiuchi Hiroshi, Chapter 5. Hereinafter, examples of the curing agentwill be shown.

Examples of a curing agent acting catalytically include tertiary aminesand boron trifluoride-amine complex, and examples of a curing agentreacting stoichiometrically with a functional group of the epoxy resininclude polyamine, acid anhydride and the like; further, examples of acuring agent performing curing at normal temperature includediethylenetriamine and polyamide resin, and examples of a curing agentperforming curing at medium temperature include diethylaminopropylamineand tris(dimethylaminomethyl)phenol; and examples of a curing agentperforming curing at high temperature include anhydrous phthalic acid,meta-phenylenediamine and the like. In addition, in terms of chemicalstructure, for amines, examples of aliphatic polyamine includediethylenetriamine; examples of aromatic polyamine includemeta-phenylenediamine; examples of tertiary amine includetris(dimethylaminomethyl)phenol; examples of acid anhydride includeanhydrous phthalic acid, a polyamide resin, a polysulfide resin and aboron trifluoride-monoethylamine complex; and examples of a syntheticresin initial condensate include a phenolic resin, dicyandiamide and thelike.

These curing agents react and polymerize with an epoxy group by heating,and thus the crosslink density is increased to achieve curing. Both thebinder and the curing agent are preferably as small in amount aspossible for achieving a thin film, and particularly, the curing agentis 35% by mass or less, preferably 30% by mass or less, and morepreferably 25% by mass or less based on the heat curable compound.

(Curing Catalyst)

Curing by reaction of epoxy mainly with each other in addition to curingby reaction with the curing agent is effective for realizing highconcentration of the coloring agent. For this reason, a curing catalystmay also be used without using the curing agent. The curing may beperformed by as slight an amount as the added amount of the curingcatalyst approximately 1/10 to 1/1000, preferably approximately 1/20 to1/500, and more preferably approximately 1/30 to 1/250 on the basis ofmass based on an epoxy resin with an epoxy equivalent weight ofapproximately 150 to 200.

(Polymerization Inhibitor)

In the coloring composition of the present invention, it is preferred toadd a small amount of polymerization inhibitor for inhibitingunnecessary thermal polymerization of the polymerizable compound duringthe preparation or the storage of the above-described coloringcomposition.

Examples of the polymerization inhibitor which may be used in thepresent invention include hydroquinone, p-methoxyphenol,di-t-butyl-p-cresol, pyrogallol, t-butyl-catechol, benzoquinone,4,4′-thiobis(3-methyl-6-t-butylphenol),2,T-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamineprimary cerium salt and the like.

The amount of the polymerization inhibitor added is preferably about0.01% by mass to about 5% by mass based on a mass of the totalcomposition.

(Silane Coupling Agent)

In the coloring composition of the present invention, a silane couplingagent may be used from the viewpoint of further improving the adhesionto a substrate.

The silane coupling agent preferably has an alkoxysilyl group as ahydrolyzable group capable of chemically bonding with an inorganicmaterial. Further, it is preferred to have a group which interacts withor form a bond with an organic resin to show affinity, and it ispreferred to have, as such a group, a (meth)acryloyl group, a phenylgroup, a mercapto group, a glycidyl group and an oxetanyl group, amongthem, it is preferred to have a (meth)acryloyl group or a glycidylgroup.

That is, as a silane coupling agent used in the present invention, acompound having an alkoxysilyl group, a (meth)acryloyl group or an epoxygroup is preferred, and specific example thereof include a(meth)acryloyl-trimethoxy silane compound having the followingstructure, a glycidyl-trimethoxysilane compound and the like.

Further, as the silane coupling agent in the present invention, a silanecompound having at least two functional groups with different reactivityin one molecule is preferred, and particularly, it is preferred to have,as the functional group, an amino group and an alkoxy group. Examples ofthe silane coupling agent includeN-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (trade name KBM-602,manufactured by SHIN-ETSU CHEMICAL CO., LTD.),N-β-aminoethyl-γ-aminopropyl-trimethoxysilane (trade name KBM-603,manufactured by SHIN-ETSU CHEMICAL CO., LTD.),N-β-aminoethyl-γ-aminopropyl-triethoxysilane (trade name KBE-602,manufactured by SHIN-ETSU CHEMICAL CO., LTD.),γ-aminopropyl-trimethoxysilane (trade name KBM-903, manufactured bySHIN-ETSU CHEMICAL CO. LTD.), γ-aminopropyl-triethoxysilane (trade nameKBE-903, manufactured by SHIN-ETSU CHEMICAL CO., LTD.) and the like.

When the silane coupling agent is used, the amount of the silanecoupling agent added is preferably 0.1% by mass to 5.0% by mass and morepreferably 0.2% by mass to 3.0% by mass, based on the total solids ofthe coloring composition used in the present invention.

<Method for Preparing Coloring Composition>

A preferred preparation method of the coloring composition in thepresent invention will be described. However, the present invention isnot limited thereto.

When the coloring composition in the present invention contains apigment as a colorant, a method for pulverizing pigment particles intofiner particles and using a pigment having a sharp particle sizedistribution is suitable. Specifically, a method for using a pigmentwhich has an average particle diameter of approximately 0.01 μm andcontains pigment particles having a particle diameter in a range of0.01±0.005 μm in an amount of 75% by mass or more is preferred. In orderto adjust the particle size distribution of a pigment in theabove-described range, a method the dispersing the pigment isparticularly important. Examples of the dispersion method include adispersion method in which dry dispersion (kneading dispersiontreatment) of performing dispersion in the high viscosity state by usinga kneader or a roll mill such as two-roll mill and wet dispersion (finedispersion treatment) of performing dispersion in the relatively lowviscosity state by using a three-roll mill, a bead mill or the like arecombined. Further, in the dispersion method, it is also preferred todisperse two or more pigments together, to use no or a minimal amount ofsolvent during kneading dispersion treatment, or to use variousdispersants. In addition, it is preferred to add the resin component intwo portions during the kneading dispersion treatment and during thefine dispersion treatment (two-portion use) in order to alleviate thesolvent shock, and it is also preferred to use a resin component whichis excellent in solubility, in order to prevent the reaggregation of thepigment particles when the processing is changed from kneadingdispersion treatment to fine dispersion treatment. Further, means ofusing high-rigidity ceramics or smaller particle diameter beads as thebeads of the bead mill used during fine dispersion treatment are alsoeffective.

In the present invention, it is preferred to use a colorant obtained byusing two or more pigments, and dispersing the two or more pigments in ahigh viscosity state of 50,000 mPa·s or more and then dispersing thepigments in a low viscosity state of 1,000 mPa·s or less.

Generally, these pigments are supplied after the pigments are dried byvarious methods after synthesis. The pigment is usually supplied aspowder by drying the pigment from an aqueous medium, but drying forpowder demands a lot of heat energy because a great latent vaporizationheat is required for water to be dried. As a result, the pigmentnormally forms an aggregate (secondary particles) in which primaryparticles are collected.

When the colorant in the preparation method of the coloring compositionis a pigment, it is preferred to first knead and disperse theabove-described binder in the colorant (pigment) such that the viscosityafter kneading dispersion treatment is a relatively high viscosity of50,000 mPa·s or more (preferably 50,000 mPa·s to 100,000 mPa·s). Herein,the kneading dispersion treatment may be high viscosity dispersion ordry dispersion. Subsequently, it is preferred to further add theabove-described binder as needed to a dispersoid after the kneadingdispersion treatment and perform a fine dispersion treatment such thatthe viscosity after the fine dispersion treatment is a relatively lowviscosity of 1000 mPa·s or less (preferably 100 mPa·s or less). Inaddition, the fine dispersion treatment may be low viscosity dispersionor wet dispersion.

In the kneading dispersion treatment, the ratio of the solvent to amaterial to be dispersed is preferably 0% by mass to 20% by mass. Thus,it is possible to promote the wetting degree of a constituting componentmainly including a vehicle resin component on the pigment particlesurface by dispersing the mixture without using much solvent, and thusit is possible to convert an interface formed by the pigment particlesurface from the solid/gas interface between the pigment particle andair to the solid/solution interface between the pigment particle andvehicle solution. It is possible to disperse the pigment into the microstate close to the primary particle thereof, by converting the interfaceformed by the pigment particle surface from air to the solution andperforming mixing/stirring.

In this way, it is effective to convert the interface formed by thepigment particle surface from air to the solution, in order to dispersethe pigment more highly. Strong shearing force or compressive force isrequired for the conversion. For this reason, it is preferable to use akneader that may exhibit strong shearing force or compressive force inthe kneading dispersion treatment, and to use high viscosity pigmentparticles as a material to be kneaded.

Further, it is preferred to mix and agitate the mixture together with adispersion medium in a fine particle state, such as glass or ceramic inthe fine dispersion treatment. In addition, the ratio of the solvent inthe fine dispersion treatment is preferably 20% by mass to 90% by massbased on the material to be dispersed. Because it is necessary touniformly and stably distribute the pigment particles into the microstate during the fine dispersion treatment, it is preferable to use adispersing machine that may impart impact and shearing forces to theaggregated pigment particles and to use low viscosity pigment particlesas a material to be dispersed.

When the colorant is a dye, the dispersion process is not needed asdescribed above, and the dye may only be dissolved in a suitable solventtogether with a binder.

In particular, it is preferred to prepare the coloring composition inthe present invention by adding the heat curable compound and a curingcatalyst or a curing agent to the pigment dispersoid or dye solutionthus obtained when the heat curable compound is an epoxy compound, oradding a curing catalyst or a curing agent thereto to impart the heatcuring function and adding a solvent thereto if necessary when thebinder is already a heat-curable compound.

<Filter Filtration>

It is preferred that the coloring curable composition of the presentinvention is filtered by a filter, for the purpose of removingimpurities or reducing defects.

As a filter for filter filtration, filters that have been used in therelated art for filtration use and the like may be used without anyparticular limitation.

Examples of a material for the filter include a fluorine resin such aspolytetrafluoroethylene (PTFE), a polyamide-based resin such as Nylon-6and Nylon-6,6; a polyolefin resin (including a high density and anultrahigh molecular weight) such as polyethylene and polypropylene (PP);and the like. Among these materials, polypropylene (including highdensity polypropylene) is preferred.

The pore diameter of the filter is not particularly limited, but is, forexample, approximately 0.01 μm to 20.0 μm, preferably approximately 0.01μm to 5 μm, and still more preferably approximately 0.01 μm to 2.0 μm.

Fine particles may be more effectively removed by adjusting the porediameter of the filter within the above-described range, therebyreducing the turbidity more.

As the pore diameter of the filter herein, a reference may be made tonominal values of a filter maker. A commercially available filter may beselected from various filters provided by, for example, PallCorporation, Toyo Roshi Kaisha, Ltd., Entegris, Inc. (formerly MykrolisCorporation), KITZ MICRO FILTER CORPORATION or the like.

In the filter filtration, a combination of two or more filters may beused.

For example, filtration is first performed by using a first filter, andsubsequently, filtration may be performed by using a second filter witha pore diameter different from the pore diameter of the first filter.

At that time, filtering at the first filter and filtering at the secondfilter may be performed once or two or more times.

As the second filter, a filter formed of a material which is the same asthe material for the above-described first filter and the like may beused.

<Color Filter and Method for Manufacturing the Same>

The color filter of the present invention is a colored pattern in whichat least one pattern of the patterns constituting the filter is formedfrom the coloring composition of the present invention as describedabove. The color filter of the present invention is not particularlylimited so long as at least one pattern is a colored pattern formed fromthe colored composition of the present invention as described above, butthe color filter is preferably manufactured by the method formanufacturing a color filter of the present invention as describedbelow.

In the method for manufacturing a color filter of the present invention,a first colored layer is formed using the coloring composition (alsoreferred as to a first coloring composition) of the present invention asdescribed above.

Here, since the first colored layer is formed by the coloringcomposition of the present invention, the solvent resistance and thealkaline developing solution resisntace are excellent.

For this reason, as described below in detail, when dissolving the firstcolored layer in a developing solution used in forming a resist pattern(patterned photoresist layer) as an etching mask on the first coloredlayer, or dissolving in an organic solvent of a second or third coloringradiation sensitive composition in the process of forming a secondcolored radiation sensitive layer with the second coloring radiationsensitive composition on the first colored layer and the process offorming a third colored radiation sensitive layer with the thirdcoloring radiation sensitive composition on the first colored layer, ordissolving a developing solution used in exposing and developing thesecond or third colored radiation sensitive layer formed with the secondor third coloring radiation sensitive composition, it is possible tosuppress a concern that color components of the first colored layer areeluted to the solvent or developing solutions, or a concern that colorcomponents of the second or third coloring radiation sensitivecomposition are mixed into the first colored layer. As a result, it ispossible to suppress the occurrence of color loss in the colored layeror the occurrence of overlap region in which a plurality of colors areoverlapped with each other, thereby improving in the performance of thecolor filter finally obtained.

In particular, the method is effective to manufacture a color filter forsolid-state imaging devices, requiring microsize such as a thickness of0.7 μm or less and/or a pixel pattern size (one side in a squarepattern) of 2 μm or less (for example, 0.5 to 2.0 μm).

Herein, the solid-state imaging device will be briefly described as anexample with reference to FIG. 1.

As illustrated in FIG. 1, a solid-state imaging device 10 is composed ofa light receiving device (photodiode) 42 installed on a siliconsubstrate, a color filter 13, a planarization film 14, a microlens 15and the like. In the present invention, it is not always necessary toinstall the planarization film 14. Meanwhile, in FIG. 1, for clarifyingeach member, the ratio of each thickness or width is ignored and eachmember is represented in a partially exaggerated manner.

A support is not particularly limited as long as the support is used ina color filter such as a silicon substrate, and examples thereof includesoda-lime glass, borosilicate glass, quartz glass, which are used in aliquid crystal display device, and the like and a product obtained byattaching a transparent conductive film thereto, or a photoelectricconversion device substrate used in a solid-state imaging device and thelike, for example, an oxide film, silicon nitride and the like. Further,an intermediate layer and the like may be installed between the supportand the color filter 13 as long as the present invention is notimpaired.

A P well 41 is formed on the silicon substrate, and the photodiode 42 isformed on a part of the surface of the P well. The photodiode 42 isformed by ion-injecting N-type impurities such as P and As into a partof the surface of the P well and then performing heat treatment. Inaddition, a region which is on the surface of the P well 41 of thesilicon substrate and is different from the part has an impuritydiffusion layer 43 which has a higher concentration of N-type impuritiesthan that of the photodiode 42. The impurity diffusion layer 43 isformed by ion-injecting N-type impurities such as P and As and thenperforming heat treatment, and the photodiode 42 serves as a floatingdiffusion layer that transfers charges generated by receiving incidentlight. Besides using the well 41 as a P-type impurity layer, and thephotodiode 42 and the impurity diffusion layer 43 as an N-type impuritylayer, the well 41 may be used as an N-type impurity layer, and thephotodiode 42 and the impurity diffusion layer 43 may be used as aP-type impurity layer.

An insulation film 47 such as SiO₂ or SiO₂/SiN/SiO₂ is formed on the Pwell 41, the photodiode 42 and the impurity diffusion layer 43, and anelectrode 44 including poly-Si, tungsten, tungsten silicide, Al, Cu andthe like is installed on the insulation film 47. The electrode 44 servesas a gate of a gate MOS transistor and may serve as a transfer gate fortransferring charges generated in the photodiode 42 to the impuritydiffusion layer 43. Further, a wiring layer 45 is formed on theelectrode 44. A BPSG film 46 and a P—SiN film 48 are further formed atan upper side of wiring layer 45. The interface of the BPSG film 46 andthe P—SiN film 48 is formed in a shape that is curved from the top tothe bottom of the photodiode 42, and thus, serves as an inlayer lens forefficiently inducing incident light into the photodiode 42. Aplanarization film layer 49 is formed on the BPSG film 46 for thepurpose of planarizing an unevenness portions other than the surface ofthe P—SiN film 48 or the pixel region.

The color filter 13 is formed on the planarization film layer 49.Meanwhile, in the following description, a colored film (so-called solidfilm) which is formed on the silicon substrate without dividing theregion refers to “a colored (colored radiation sensitive) layer” and acolored layer which is formed to divide the region in a pattern shape(for example, a film patterned in a stripe shape and the like) refers to“a colored pattern”. In addition, in the colored pattern, a coloredpattern (for example, a colored pattern patterned in a square orrectangular shape, and the like) composed of an element whichconstitutes the color filter 13 refers to “a colored (red, green andblue) pixel”.

The color filter 13 is composed of a plurality of green pixels (firstpixel) 20G, red pixels (second pixel) 20R and blue pixels (third pixel)20B, which are two-dimensionally arranged. Each of the colored pixels20R, 20G and 20B is formed above the photodiode 42, respectively. Thegreen pixels 20G are formed in a check pattern, and blue pixels 20B andred pixels 20R are formed between each of the green pixels 20G.Meanwhile, in FIG. 1, in order to explain that the color filter 13 iscomposed of three-colored pixels, each of the colored pixels 20R, 20Gand 20B is illustrated as being parallelly arranged in a row.

The planarization film 14 is formed to cover the top surface of thecolor filter 13, and planarizes the surface of the color filter.

The microlens 15 is a condenser lens, in which the convex side isdisposed upwardly, and are provided in the upper side of the planarizedfilm 14 (a color filter when not having a planarized film), and also inthe upper side of the light receiving device 42. Each microlens 15efficiently guides light from a subject to each light receiving device42.

Next, the method for manufacturing the color filter with respect to theexemplary embodiment of the present invention will be described.

In the method for manufacturing the color filter with respect to theexemplary embodiment of the present invention, the colored layer 11 isfirst formed with the first coloring composition (Process (a)), asillustrated in the schematic cross-sectional view of FIG. 2. Here, thefirst coloring composition is the coloring composition as alreadydescribed above.

The preferred form of the first colored layer 11 is a green transmittinglayer, and thus the colorant in the first coloring composition ispreferably one or more selected from C.I. Pigment Green 7, 10, 36, 37and 58, and C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14,15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40,42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95,97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118,119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150,151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170,171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188,193, 194, 199, 213 and 214.

The first colored layer 11 may be formed by coating the coloringcomposition on the support by a coating method such as a spin coating, aslit coating and a spray coating, and drying.

Herein, the thickness of the first colored layer 11 is preferably 0.3 μmto 1 μm, more preferably 0.35 μm to 0.8 μm, and still more preferably0.35 μm to 0.7 μm.

When the first coloring composition contains a curable compound, it ispreferred to cure the first colored layer 11 by heating with a heatersuch as a hot plate and an oven. The heating temperature is preferably120° C. to 250° C., and more preferably 160° C. to 230° C. Although theheating time varies depending on the heating means, the heating time isgenerally 3 minutes to 30 minutes when heating on a hot plate, andgenerally 30 minutes to 90 minutes when heating in an oven.

Subsequently, patterning is performed by dry etching to form a group ofthrough-holes in the first colored layer (Process (b)). Accordingly, afirst colored pattern is formed. By this technique, it is possible tomore reliably provide a group of through-holes having a desired shape,as compared with the case of providing a group of through-holes byforming a first colored layer with a coloring radiation sensitivecomposition, and exposing and developing the first colored layer. Thereason is that, in a coloring radiation sensitive composition having thecontent of a colorant of 50% by mass or more based on the total solidsof the composition, there is a limited choice to add components capableof contributing to developing performances in the composition, and thus,it becomes difficult to ensure reliable patterning.

The first colored pattern may be a colored pattern formed as a firsttint on a support, and if necessary, may be a colored pattern providedas a pattern, for example, after a second tint or a third tint on asupport having a pattern previously formed.

Dry etching may be performed on the first colored layer 11 using apatterned photoresist layer as a mask, and an etching gas. For example,as illustrated in the schematic cross-sectional view of FIG. 3, aphotoresist layer 51 is first formed on the first colored layer 11.

Specifically, a positive or negative type radiation sensitivecomposition is coated on the colored layer, and dried to form aphotoresist layer. In forming the photoresist layer 51, it is preferredto perform a pre-baking again. Especially, as a process of forming aphotoresist, post-exposure baking (PEB) and post-development baking(post-baking) may preferably preferred.

As a photoresist, for example, a positive type radiation sensitivecomposition is used. Examples of the positive type radiation sensitivecomposition include a positive type radiation sensitive compositonsensitive to radiations such as far-ultraviolet rays includingultraviolet rays (g-rays, h-rays and i-rays), excimer laser and thelike, electron beam and X-rays. Of radiations, g-rays, h-rays and i-raysare preferred, and among them, i-rays are more preferred.

Specifically, as the positive type radiation sensitive composition, acomposition containing a quinonediazide compound and an alkali solubleresin is preferred. In the positive type radiation sensitive compositioncontaining a quinonediazide compound and an alkali soluble resin, aquinonediazide group is decomposed by irradiating light having awavelength of 500 nm or less to produce a carboxyl group, and as aresult, the composition is converted from the alkali insoluble state tothe alkali soluble state. The positive type photoresist hassignificantly excellent resolution, and thus, is used in the manufactureof an integrated circuit such as IC or LSI. Examples of thequinonediazide compound include naphthoquinonediazide compounds.

The thickness of the photoresist layer 51 is preferably 0.1 μm to 3 μm,more preferably 0.2 μm to 2.5 μm, and still more preferably 0.3 μm to 2μm. Meanwhile, the coating of the photoresist layer 51 may be suitablyperformed by using the coating method in the first colored layer 11 asdescribed above.

Subsequently, as illustrated in the schematic cross-sectional view ofFIG. 3, a resist pattern (patterned photoresist layer) 52 having aplurality of resist through-holes 51A formed is formed by exposing anddeveloping the photoresist layer 51.

The formation of the resist pattern 52 is not particularly limited, andmay be performed by suitably optimizing a photolithography technologyknown in the related art. A plurality of resist through-holes 51A isformed in the photoresist layer 51 by exposure and development, and thusa resist pattern 52 as an etching mask used in the next etching isformed on the first colored layer 11.

The exposing of the photoresist layer 51 may be performed by exposing apositive type or negative type radiation sensitive composition tog-rays, h-rays, i-rays and the like, and preferably i-rays, through apredetermined mask pattern. After the exposure, the photoresist isremoved in accordance with a region on which a colored pattern is to beformed, by developing with a developer.

As the developer, any developer may be used as long as the developerdoes not affect a first colored layer including a colorant and dissolvesan exposed portion of the positive resist and an uncured portion of thenegative resist, and for example, a combination of various organicsolvents or an alkaline aqueous solution may be used. As the alkalineaqueous solution, an alkali aqueous solution prepared by dissolving thealkaline compound so as to have a concentration of 0.001% by mass to 10%by mass and preferably 0.01% by mass to 5% by mass is suitable. Examplesof the alkaline compound include sodium hydroxide, potassium hydroxide,sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia,ethylamine, diethylamine, dimethylethanolamine, tetramethylammoniumhydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine,1,8-diazabicyclo-[5.4.0]-7-undecene and the like. Meanwhile, when thealkaline aqueous solution is used as a developer, a washing treatment isgenerally performed with water after the development.

Next, as illustrated in the schematic cross-sectional view of FIG. 5,patterning is performed using the resist pattern 52 as an etching maskby dry etching to form a group of through-holes 120 in the first coloredlayer 11. Accordingly, the first colored pattern 12 is formed. Here, thegroup of through-holes 120 includes a first partial group ofthrough-holes 121 and a second partial group of through-holes 122.

The group of through-holes 120 is provided as a checker shape in thefirst colored layer. Therefore, the first colored patter 12, which ismade by providing the group of through-holes 120 in the first coloredlayer 11, is provided with a plurality of squre-shaped first coloredpixels as a checker shape.

Specifically, dry etching is performed by dry etching the first coloredlayer 11 using the resist pattern 52 as an etching mask. Representativeexamples of the dry etching include methods as described in JapanesePatent Application Laid-Open Nos. S59-126506, 59-46628, 58-9108,58-2809, 57-148706, 61-41102 and the like.

From the viewpoint of forming the pattern cross-section in a shapecloser to a rectangular shape or from the viewpoint of reducing thedamage to the support more than ever, it is preferred that dry etchingis performed in the following form.

A preferred aspect includes a first step etching which uses a mixed gasof a fluorine-based gas and an oxygen gas (O₂) to perform an etching upto a region (depth) in which the support is not exposed, a second stepetching which uses a mixed gas of a nitrogen gas (N₂) and an oxygen gas(O₂) to perform an etching preferably to the vicinity of a region(depth) in which the support is exposed, after the first step etching,and an overetching performed after the support is exposed. Hereinafter,a specific technique of dry etching, the first step etching, the secondstep etching and the overetching will be described.

The dry etching is performed under the etching conditions previouslyobtained by the following technique.

(1) Each of an etching rate (nm/min) in the first step etching and anetching rate (nm/min) in the second step etching is calculated.

(2) Each of a time for etching a desired thickness in the first stepetching and a time for etching a desired thickness in the second stepetching is calculated.

(3) The first step etching is performed according to the etching timecalculated in (2).

(4) The second step etching is performed according to the etching timecalculated in (2). Otherwise, the etching time may be determined fromthe detection of an end point to perform the second step etchingaccording to the etching time determined.

(5) An overetching time is calculated for the total time of (3) and (4)to perform the overetching.

From the viewpoint of processing an organic material, which is a film tobe etched, into a rectangular shape, the mixed gas used in the firststep etching process preferably includes a fluorine-based gas and anoxygen gas (O₂). Further, in the first step etching process, the damageto the support may be avoided by performing etching up to a region inwhich the support is not exposed.

In addition, in the second step etching process and the overetchingprocess, from the viewpoint of avoiding the damage to the support afteretching is performed up to a region in which the support is not exposed,by a mixed gas of a fluorine-based gas and an oxygen gas in the firststep etching process, the etching treatment is preferably performed byusing the mixed gas of the nitrogen gas and the oxygen gas.

It is important to determine a ratio of an etching amount in the firststep etching process and an etching amount in the second step etchingprocess such that the rectangularity is not impaired by the etchingtreatment in the first step etching process. Meanwhile, in the totaletching amount (the sum of the etching amount in the first step etchingprocess and the etching amount in the second step etching process), theratio of the latter is preferably more than 0% and 50% or less, and morepreferably 10% to 20%. The etching amount refers to an amount calculatedfrom a difference between a film thickness remaining in the film to beetched and a film thichness before being etched.

Further, the etching preferably includes the overetching treatment. Theoveretching treatment is preferably performed by setting an overetchingratio. In addition, the overetching ratio is preferably calculated froma treatment time of etching which is initially performed. Theoveretching ratio may be arbitrarily set, but is preferably 30% or lessof the etching treatment time in the etching process, more preferably 5%to 25% and particularly preferably 10% to 15% from the viewpoint ofmaintaining the etching resistance of the photoresist and therectangularity of a pattern to be etched.

Subsequently, as illustrated in the schematic cross-sectional view ofFIG. 6, the resist pattern (that is, etching mask) 52 remaining afterthe etching is preferably removed. The removing of the resist pattern 52preferably includes a process of imparting a stripping solution or asolvent on the resist pattern 52 to make a state capable of removing theresist pattern 52, and a process of removing the resist pattern 52 usinga washing water.

Examples of the process of imparting a stripping solution or a solventon the resist pattern 52 to make a state of capable of removing theresist pattern 52 include a process of imparting a stripping solution ora solvent at least on the resist pattern 52 and allowing the strippingsolution or the solvent to stand for a predetermined time to perform apuddle development. A time for allowing the stripping solution or thesolvent to stand is not particularly limited, but is preferably severaldozen seconds to several minutes.

Further, examples of the process of removing the resist pattern 52 usinga washing water include a process of spraying a washing water on theresist pattern 52 from a spray type or shower type spray nozzle toremove the resist pattern 52. As the washing water, pure water may bepreferably used. In addition, examples of the spray nozzle include aspray nozzle allowing the entire support to be included in the sprayrange, or a movable spray nozzle in which the movable range thereofinclude the entire support. When the spray nozzle is movable, the resistpattern 52 may be more effectively removed by moving the spray nozzlefrom the central portion of the support to the end portion of thesupport twice or more during the process of removing the resist pattern52 to spray the washing water.

The stripping solution generally contains an organic solvent, but mayfurther contain an inorganic solvent. Examples of the organic solventinclude 1) hydrocarbon-based compounds, 2) halogenated hydrocarbon-basedcompounds, 3) alcohol-based compounds, 4) ether- or acetal-basedcompounds, 5) ketone- or aldehyde-based compounds, 6) ester-basedcompounds, 7) polyhydric alcohol-based compounds, 8) carboxylic acid orcarboxylic anhydride-based compounds, 9) phenolic compounds, 10)nitrogen-containing compounds, 11) sulfur-containing compounds and 12)fluorine-containing compounds. The stripping solution preferablycontains a nitrogen-containing compound and more preferably includes anacyclic nitrogen-containing compound and a cyclic nitrogen-containingcompound.

The acyclic nitrogen-containing compound is preferably an acyclicnitrogen-containing compound having a hydroxyl group. Specific examplesthereof include monoisopropanolamine, diisopropanolamine,triisopropanolamine, N-ethylethanolamine, N,N-dibutylethanolamine,N-butylethanolamine, monoethanolamine, diethanolamine, triethanolamineand the like, monoethanolamine, diethanolamine and triethanolamine arepreferred and monoethanolamine (H₂NCH₂CH₂OH) is more preferred. Further,examples of the cyclic nitrogen-containing compound includeisoquinoline, imidazole, N-ethylmorpholine, ε-caprolactam, quinoline,1,3-dimethyl-2-imidazolidinone, α-picoline, β-picoline, γ-picoline,2-pipecholine, 3-pipecholine, 4-pipecholine, piperazine, piperidine,pyrazine, pyridine, pyrrolidine, N-methyl-2-pyrrolidone,N-phenylmorpholine, 2,4-lutidine, 2,6-lutidine and the like, preferablyN-methyl-2-pyrrolidone and N-ethylmorpholine, and more preferablyN-methyl-2-pyrrolidone (NMP).

The stripping solution preferably contains an acyclicnitrogen-containing compound and a cyclic nitrogen-containing compound,and among them, more preferably contains at least one selected frommonoethanolamine, diethanolamine and triethanolamine as the acyclicnitrogen-containing compound and at least one selected fromN-methyl-2-pyrrolidone and N-ethylmorpholine as the cyclicnitrogen-containing compound, and still more preferably containsmonoethanolamine and N-methyl-2-pyrrolidone.

When removing with a stripping solution, the resist pattern 52 formed onthe first colored pattern 12 may be removed, and even when a depositedmaterial which is an etching product is attached on the sidewall of thefirst colored pattern 12, the deposited material may not be completelyremoved. The deposited material refers to an etching product attachedand accumulated on the sidewall of the colored layer.

As the stripping solution, it is preferred that the content of theacyclic nitrogen-containing compound is 9 parts by mass to 11 parts bymass based on 100 parts by mass of the stripping solution and thecontent of the cyclic nitrogen-containing compound is 65 parts by massto 70 parts by mass based on 100 parts by mass thereof. In addition, thestripping solution is preferably a mixture of an acyclicnitrogen-containing compound and a cyclic nitrogen-containing compounddiluted with pure water.

Sequently, as illustrated in the schematic cross-sectional view of FIG.7, a second colored radiation sensitive layer 21 is stacked with asecond coloring radiation sensitive composition on the first coloredlayer (that is, the first colored pattern 12 which is made by formingthe group of through-holes 120 in the first colored layer 11) such thatthe second coloring radiation sensitive composition is embedded insideeach of the through-holes in the first through-holes 121 and the secondthrough-holes 122 so as to form a plurality of third colored pixels(Process (c)). Accordingly, a second colored pattern 22 is formed, whichhas a plurality of the second colored pixels in the through-holes 120 ofthe first colored layer 11. Here, the second colored pixels are made upof square shaped Pixels. The formation of the second colored radiationsensitive layer 21 may be conducted in the same manner as the method forforming the first colored layer 11 as described above.

Herein, the thickness of the second colored radiation sensitive layer 21is preferably 0.3 μm to 1 μm, more preferably 0.35 μm to 0.8 μm, andstill more preferably 0.35 μm to 0.7 μm.

And, the second colored radiation sensitive layer 21, and a plurality ofthe second colored pixels 22R formed inside each of the through-holes inthe second partial group of through-holes 122 are removed by exposingand developing the position 21A of the second colored radiationsensitive layer 21 which corresponds to the first partial group ofthrough-holes 121 formed in the first colored layer 11 (Process (d))(see the schematic cross-sectional view of FIG. 8).

Subsequently, as illustrated in the schematic cross-sectional view ofFIG. 9, a third colored radiation sensitive layer 31 is formed with athird coloring radiation sensitive composition on the first coloredlayer (that is, the first colored pattern 12 which is made by formingthe through-holes 120 in the first colored layer 11) such that the thirdcoloring radiation sensitive composition is embedded inside each of thethrough-holes in the second through-holes 122 so as to form a pluralityof third colored pixels (Process (e)). Accordingly, a third coloredpattern 32 is formed, which has a plurality of the third colored pixelsin the second through-holes 122 of the first colored layer 11. Here, thethird colored pixels are made up of square shapedpixels. The formationof the third colored radiation sensitive layer 31 may be done in thesame manner as the method for forming the first colored layer 11 asdescribed above.

Herein, the thickness of the third colored radiation sensitive layer 31is preferably 0.3 μm to 1 μm, more preferably 0.35 μm to 0.8 μm, andstill more preferably 0.35 μm to 0.7 μm.

And, a color filter 100 having the first colored patterns 12, the secondcolored patterns 22 and the third colored patterns, as illustrated inthe schematic cross-sectional view of FIG. 10, is manufactured byremoving the third colored radiation sensitive layer 31 by exposing anddeveloping the position 31A of the third colored radiation sensitivelayer 31 which corresponds to the second through-holes 122 formed in thefirst colored layer 11 (Process (f)).

Each of the above-described second coloring composition and thirdcoloring radiation sensitive composition contains a colorant. Thecolorant may be exemplified as described above in the coloringcomposition of the present invention, but is preferably a redtransmitting portion or a blue transmitting portion, respectivelybecause it is preferred that one of the second colored pixel and thethird colored pixel is a red transmitting portion and the other is ablue transporting portion. A colorant to be contained in a coloringcomposition for forming a red transmitting portion is preferably one ormore selected from C.I. Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36,38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71 and 73, and C.I.Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41,48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1,63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123,144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177,178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210,216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272 and 279, and acolorant to be contained in a coloring composition for forming a bluetransmitting portion is preferably one or more selected from C.I.Pigment Violet 1, 19, 23, 27, 32, 37 and 42, and C.I. Pigment Blue 1, 2,15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66, 79 and 80.

In each of the second coloring radiation sensitive composition and thethird coloring radiation sensitive composition, the content of thecolorant is preferably 30% by mass or more, more preferably 35% by massor more, and still more preferably 40% by mass or more based on thetotal solids of the composition. In addition, the content of thecolorant is generally 90% by mass or less, and preferably 80% by mass orless.

Further, for each of the second coloring radiation sensitive compositionand the third coloring radiation sensitive composition, a negative typeradiation sensitive composition is preferably used. Examples of thenegative type radiation sensitive composition include a negative typeradiation sensitive compositon sensitive to radiations such asfar-ultraviolet rays including ultraviolet rays (g-rays, h-rays andi-rays), excimer laser and the like, electron beam and X-rays. Ofradiations, g-rays, h-rays and i-rays are preferred, and among them,i-rays are more preferred.

Specifically, as the negative type radiation sensitive composition, acomposition containing a photopolymerization initiator, a polymerizationcomponent (polymerizable compound), a binder resin (alkali soluble resinand the like) and the like is preferred, and examples thereof includecompositions as described, for example, in paragraph Nos. [0017] to[0064] of Japanese Patent Application Laid-Open No. 2005-326453. Thesenegative type radiation sensitive compositions allow aphotopolymerization initiator to initiate the polymerization reaction ofa polymerizable compound by irradiation of radiation, and as a result,the composition is converted from an alkali soluble state to an alkaliinsoluble state.

The exposure of the second colored radiation sensitive layer 21 and thethird colored radiation sensitive layer 31 may be performed by exposingwith g-rays, h-rays, i-rays and the like.

In addition, the development performed after exposure is performed bydeveloping with a developing solution.

The developing solution may be exemplified by the same developingsolution as described in exposure and development of photoresist layer51.

Further, when an alkaline aquous solution is used as a developingsolution, washing with water is generally performed after developing.

In the first colored pixels, the second colored pixels and the thirdcolored pixels, the length of one side (it indicates a length of ashorter side when the pixel is rectangular, or a length of one side whenthe pixel is square) is preferably 0.5 μm to 1.7 μm, more preferably 0.6μm to 1.5 μm from the viewpoint of image resolution.

According to the method for manufacturing a color filter of the presentinvention as described above, since the first colored layer, that is,the first colored pixel is formed with a coloring composition havinghigh concentration of a colorant, the thickness of the first pixel canbe made very thin (for example, 0.7 μm or less). Accordingly, a colorfilter in which crosstalk (color mixing of light) is suppressed can bemanufactured with the method.

Further, the first pixel formed with the coloring composition of thepresent invention has excellent solvent resistance and alkalinedeveloping solution resistance, as described above. Accordingly, theoccurrence of overlap region overlapped with colors in other coloredlayers and other colored patterns may be reduced, and as a result, ahigh performance color filter may be prepared.

A color filter obtained from the coloring composition of the presentinvention may be suitably used for a liquid crystal display device (LCD)or a solid-state imaging device (for example, CCD, CMOS and the like).Further, the color filter may also be suitably used for an image displaydevice such as electronic paper or organic EL. In particular, the colorfilter of the present invention may be suitably used for a solid-stateimaging device such as a CCD and a CMOS.

The color filter of the present invention is appropriate as a colorfilter for a liquid crystal display device. A liquid crystal displaydevice equipped with the color filter may display high-quality imageshaving good tint of the display image and excellent displaycharacteristics.

Definitions of the display device or details of each display device aredescribed in, for example, “Electronic Display Device” (written bySasaki Akio, Kogyo Chosakai Publishing Co., Ltd., published in 1990),“Display Device” (written by Ibuki Sumiaki, Sangyo Tosho Publishing Co.,Ltd., published in 1989) and the like. Further, liquid crystal displaydevices are described in, for example, “Next Generation Liquid CrystalDisplay Techniques” (edited by Uchida Tatsuo, Kogyo Chosakai PublishingCo., Ltd., published in 1994). The liquid crystal display device towhich the present invention may be applied is not particularly limited,and the present invention may be applied to, for example, liquid crystaldisplay devices of various modes, as described in the above-described“Next Generation Liquid Crystal Display Techniques”.

A color filter of the present invention is useful for liquid crystaldisplay devices in a color TFT system. Details of liquid crystal displaydevices of color TFT system are described in, for example, “Color TFTLiquid Crystal Display (published by Kyoritsu Shuppan Co., Ltd. in1996)”. Further, the present invention may be applied to liquid crystaldisplay devices having an enlarged view angle such as a transversalelectric field driving system such as IPS, a pixel division system suchas MVA, or also to STN, TN, VA, OCS, FFS, R-OCB and the like.

Further, the color filter of the present invention may also be providedto a color-filter on array (COA) system with brightness and highdefinition.

In a colored layer farmed by the COA system, it is necessary to form aconduit such as a rectangular through-hole or a U-shaped concave portionhaving a side length of approximately 1 μm to 15 μm in order toestablish electrical communication between an ITO electrode disposed ona colored layer and a terminal of a driving substrate below the coloredlayer, and the size (that is, the side length) of the conduit isparticularly preferably 5 μm or less, but it is also possible to form aconduit of 5 μm or less by using the present invention. These imagedisplay systems are described in, for example, “EL, PDP, LCDDisplays—Current Trend of Techniques and Markets—(Investigative ResearchDepartment, Toray Research Center, Inc., published in 2001)”, page 43and the like.

The liquid crystal display device of the present invention is composedof the color filter of the present invention and other various memberssuch as an electrode substrate, a polarizing film, a phase differencefilm, a backlight, a spacer, a viewing angle securing film and the like.The color filter of the present invention may be applied to liquidcrystal display devices composed of these known members. Details ofthese members are described in, for example, “'94 Markets of PeripheralMaterials and Chemicals for Liquid Crystal Displays” (Shima Kentaro,published by CMC Publishing Co., Ltd. in 1994) and “2003 Current Statusand Future Outlook of Liquid Crystal Related Market (Second Volume)(Omote Ryokichi, published by Fuji Chimera Research Institute Inc. in2003).

Details about backlights are described in SID Meeting Digest 1380 (2005)(A. Konno et al.), Monthly Display, December issue, 2005, pages 18 to 24(Shima Yasuhiro), pages 25 to 30 (Yagi Takaaki) and the like.

When the color filter of the present invention is used in a liquidcrystal display device, a high contrast may be implemented when combinedwith a three-wavelength tube of a cold-cathode tube known in the relatedart. Furthermore, the use of LED light sources (RGB-LED) of red, green,and blue colors as backlights may provide a liquid crystal displaydevice having high luminance intensity and good reproducibility ofcolors with high color purity.

EXAMPLE

Hereinafter, the present invention will be specifically described withreference to Examples, but the present invention is not limited to theExamples. Further, unless particularly specified, “parts” and “%” are bymass. In addition, when a commercially available treatment liquid isused to perform a treatment in each process, each treatment is performedby a method designated by a maker unless otherwise specified.

Examples 1 to 54, Comparative Examples 1 to 2 Example 19 Preparation ofPigment Dispersion Liquid

—Preparation of Green Pigment Dispersion Liquid—

A mixed solution including 8.6 parts of Pigment Green 36, which is aphthalocyanine pigment, and 5.7 parts of Pigment Yellow 185 as pigments,1.4 parts of Derivative A as a pigment derivative, 4.3 parts ofDispersant A as a dispersion resin and 80 parts of propylene glycolmonomethyl ether acetate (PGMEA) as a solvent, was mixed and dispersedfor 15 hours with a bead mill to prepare a green pigment dispersionliquid.

Preparation of Green Pigment-Containing Composition (Coating Solution)

Using the green pigment dispersion liquid as described above, mixing andstirring was carried out so as to have the following composition toprepare a green curable composition.

Composition

Pigment dispersion liquid: the green pigment dispersion liquid 85.0parts Curable compound: Additive A 3.24 parts Solvent: PGMEA 8.76 partsSurfactant: F-781 (manufactured by DIC Corporation)  3.0 parts(polymer-type surfactant: mass average molecular weight 30,000, solidacid nuber 0 mg KOH/g), 0.2% solution in PGMEA)

Examples 1 to 18 and 20 to 54, Comparative Examples 1 to 2

Coloring curable compositions are prepared by changing the kinds ofpigments, pigment derivatives, dispersion resins and curable compoundsinto the kinds thereof described in Table 1 and Table 2 in Examples andComparative Examples which are all the same as Example 19 in terms ofpigment concentrations (contents based on the total solids of thecoloring curable composition) and D/P values (mass ratio of dispersionresin/pigment).

In Examples which are different from Example 19 in terms of D/P values,coloring curable compositions are prepared in the same manner as inExample 19, except that the kinds of pigments, pigment derivatives,dispersion resins and curable compounds are changed into the kindsthereof in Table 1 and Table 2, the amounts of the dispersion resins arechanged so as to obtain D/P values described in Table 1 and Table 2, andthe amounts of the curable compounds are adjusted to obtain valuesdescribed in Table 1 and Table 2 as the concentrations of the pigmentsbased on the total solids of the coloring curable compositions.

In Examples where D/P values are the same as those of Example 19 but theconcentrations of the pigments are different, coloring curablecompositions are prepared in the same manner as in Example 19, exceptthat the kinds of pigments, pigment derivatives, dispersion resins andcurable compounds are changed into the kinds thereof in Table 1 andTable 2 and the amounts of the curable compounds are adjusted to obtainvalues described in Table 1 and Table 2 as the concentrations of thepigments based on the total solids of the coloring curable compositions.

Further, in Examples and Comparative Examples, dispersants having asolid acid value described in the following Table were used.

Evaluation of Coloring Composition (1) (Dispersion Stability)

Immediately after preparing each of the green coloring curablecompositions of Examples and Comparative Examples in the manner asdescribed above, the initial viscosity of the coloring curablecomposition at 25° C. was measured using a viscometer (RE85L,manufactured by TOKI SANGYO CO., LTD.). The coloring curable compositionwas stored at 45° C. for three days, and then, the viscosity at 25° C.was measured again using the same viscometer (hereinafter, referred asto “viscosity after elapsed time”).

The dispersion stability was evaluated under the following evaluationcriteria.

[Evaluation Criteria]

A: [Viscosity after elapsed time/Initial viscosity]=1.0 or more and lessthan 1.10

B: [Viscosity after elapsed time/Initial viscosity]=1.10 or more andless than 1.20

C: [Viscosity after elapsed time/Initial viscosity]=1.20 or more andless than 1.50

D: [Viscosity after elapsed time/Initial viscosity]=1.50 or more

(Solvent Resistance and Alkaline Developing Solution Resistance)

Each of the green coloring curable compositions of Examples andComparative Examples obtained above, was coated on a glass wafer to adry film thickness of 0.55% n by using a spin coater, and heated on ahot plate at 200° C. for 300 seconds.

To the green color filter obtained above, propylene glycol monomethylether acetate (PGMEA), acetone, N-methylpyrrolidone (NMP), photoresiststripping solution MS230C (manufactured by FUJIFILM ELECTRONIC MATERIALSCO., LTD.) and alkaline developing solution FHD-5 (tetramethylammoniumhydroxide (TMAH): 2.38% by mass, manufactured by FUJIFILM ELECTRONICMATERIALS CO., LTD.) were added dropwise, respectively, followed byallowing to stand for 120 seconds and rinsing with running water for 10seconds.

The spectral variance of the transmittance before and after addingdropwise various liquids was measured using MCPD-3000 (manufactured byOTSUKA ELECTRONICS CO., LTD.), and the color difference ΔEab wasmeasured. The corresponding ΔEab with respect to the liquids having thelargest ΔEab was shown in Tables 1 and 2.

As the ΔEab is lower, it means that the solvent resistance and thealkaline developing solution resistance are more excellent.

The result of the avobe evaluation is shown in the following tables.

TABLE 1 Solid acid Pigment number Solvent resistance• Mass concentrationPigment Dispersion (mg Curable Dispersion alkaline developing Pigmentratio (% by mass) D/P derivative resin KOH/g) compound stabilitysolution resistance Example 1 G36/Y139 60/40 70 0.3 Derivative ADispersant A 30 Additive A A 0.6 Example 2 G36/Y150 60/40 70 0.3 A 0.6Example 3 G36/Y185 60/40 50 0.3 A 0.7 Example 4 55 0.3 A 0.5 Example 560 0.4 A 0.5 Example 6 60 0.3 Derivative B Dispersant B 0 A 1.5 Example7 Dispersant D 0 A 1.5 Example 8 Dispersant E 10 A 1.5 Example 9 30 A1.5 Example 10 60 B 2.0 Example 11 Dispersant F 0 A 1.5 Example 12Derivative A Dispersant A 10 Additive A A 0.2 Example 13 Additive B A0.3 Example 14 Additive C A 0.5 Example 15 Additive D A 0.5 Example 16Additive E A 0.5 Example 17 Additive F A 0.5 Example 18 G36/Y185 60/4060 0.3 Derivative A Dispersant A 10 Additive G A 0.5 Example 19 30Additive A A 0.2 Example 20 Additive B A 0.3 Example 21 Additive C A 0.5Example 22 Additive D A 0.5 Example 23 Additive E A 0.5 Example 24Additive F A 0.5 Example 25 Additive G A 0.5 Example 26 60 Additive A B0.2 Example 27 Additive B B 0.3 Example 28 Additive C B 0.6 Example 29Additive D B 0.6 Example 30 Additive E B 0.6 Example 31 Additive F B 0.6Example 32 Additive G B 0.6

TABLE 2 Solid acid Pigment number Solvent resistance• Mass concentrationPigment Dispersion (mg Curable Dispersion alkaline developing Pigmentratio (% by mass) D/P derivative resin KOH/g) compound stabilitysolution resistance Example 33 G36/Y185 60/40 60 0.3 Derivative ADispersant C 10 Additive A A 0.6 Example 34 30 A 0.6 Example 35 60 B 1.0Example 36 Dispersant E 10 A 0.6 Example 37 30 A 0.6 Example 38 60 B 1.0Example 39 Derivative C Dispersant A 30 B 1.2 Example 40 Dispersant C 30B 1.2 Example 41 Dispersant E 30 B 1.2 Example 42 70 0.35 Derivative ADispersant A 30 A 0.2 Example 43 80 0.2 A 0.2 Example 44 G58/Y139 60/4070 0.3 A 0.8 Example 45 G58/Y150 60/40 70 0.3 A 0.8 Example 46 G58/Y18560/40 70 0.3 A 0.8 Example 47 G36/G7/ 80/10/ 70 0.3 A 0.8 Y139 10Example 48 G36/G7/ 60/10/ 70 0.3 A 0.8 Y139/Y185 20/10 Example 49G36/Y150/ 80/10/ 70 0.3 A 0.8 Y139 10 Example 50 G36/Y150/ 80/10/ 70 0.3Derivative A Dispersant A 30 Additive A A 0.8 Y185 10 Example 51G58/Y150/ 80/10/ 70 0.3 A 0.8 Y139 10 Example 52 G58/Y150/ 80/10/ 70 0.3A 0.8 Y185 10 Example 53 G36 100 70 0.3 A 0.3 Example 54 G58 100 70 0.3A 0.3 Compar- G36/Y185 60/40 60 0.3 Derivative A Dispersant A 90Additive A D 4.0 ative Example 1 Compar- 100 D 4.0 ative Example 2

The abbreviations and compounds listed in Tables 1 and 2 are as follows.

(Colorant)

G7: C.I. Pigment Green 7

G36: C.I. Pigment Green 36

G58: C.I. Pigment Green 58

Y139: C.I. Pigment Yellow 139

Y150: C.I. Pigment Yellow 150

Y185: C.I. Pigment Yellow 185

(Pigment Derivatives)

(Dispersant)

Among the following exemplary compounds (except Dispersant A), thenumerical value written in each of the structural units (the numericalvalue written in the repeating units of the main chain) represents thecontent of the corresponding structural unit [in % by mass (wt %)]. Thenumerical value written in the repeating units of the side chainsrepresents a repeating number of the corresponding repeating moiety. Inaddition, a and b in Dispersant A represent the number of partialstructures in brackets, and satisfy a+b=6.

(Curable Compound)

As shown in Tables 1 and 2, it is understood that the coloringcompositions of Examples, in which the maximum solid acid number is 80mg KOH/g or less, are excellent in dispersion stability, solventresistance and alkaline developing solution resistance.

Further, in the above Examples, even when the pigment species is changedto a pigment mixture of C.I. Pigment Blue 15:6 and C.I. Pigment Violet23 in a mass ratio of 80:20, and to a pigment mixture of C.I. PigmentRed 254 and C.I. Pigment Yellow 139 in a mass ratio of 75:25, the resultwas obtained that dispersion stability, solvent resistance and alkalinedeveloping solution resistance are excellent.

Evaluation for Solvent Resistance Test

The coloring composition of Examples 39 and 40 was coated on a glasssubstrate to a film thickness of 0.6 μm by using a spin coater, and issubjected to heat treatment (pre-bake) with a hot plate at 100° C. for120 seconds. Subsequently, heat treatment (post-bake) was performed witha hot plate at 200° C. for 300 seconds to prepare a hardened film.

The transmittance of the color filter thus obtained was measured at awavelength region of 300 nm to 800 nm by a spectrophotometer (ref. glasssubstrate), which is a UV/VIS/NIR spectrophotometer, UV3600(manufactured by SHIMADZU CORPORATION). In addition, differentialinterference images were observed through reflective observation (50×magnifications) by using an optical microscope, BX60 manufactured byOLYMPUS.

Subsequently, the filter was immersed in the following solvent for 5minutes, dried and then, the film surface was observed again byspectrometry and an optical microscope, and the variance (a valuerepresented by an equation |T₀−T₁, wherein T₀ represents thetransmittance before solvent immersion and T₁ represents thetransmittance after solvent immersion) of the transmittance before andafter solvent immersion and the film surface failure were evaluated.

(Solvent Used)

Propylene glycol monomethyl ether acetate,

Acetone,

Alkaline Developer FHD-5 (manufactured by FUJIFILM ELECTRONIC MATERIALSCO., LTD.),

N-methyl-2-pyrrolidone

Evaluation

(Spectral Variation Before and after Solvent Immersion)

Evaluation Criteria

AA: Good The variance of the transmittance at 300 nm to 800 nm beforeand after solvent immersion is less than 2%

A: Slightly good The variance of the transmittance at 300 nm to 800 nmbefore and after solvent immersion is 2% or more and less than 5%

B: Sufficient The variance of the transmittance at 300 nm to 800 nmbefore and after solvent immersion is 5% or more and less than 10%

C: Insufficient The variance of the transmittance at 300 nm to 800 nmbefore and after solvent immersion is more than 10%

Among the above four solvents, the worst evaluation is regarded as theevaluation of the corresponding example.

(Visual Evaluation Before and after Solvent Immersion)

Evaluation Criteria

AA: Good Not changed

A: Slightly good Almost not changed

B: Sufficient Surface roughness partially observed

C: Insufficient Surface roughness observed

Among the above four solvents, the worst evaluation is regarded as theevaluation of the corresponding example.

The samples of Examples were evaluated relative to the solventresistance as well as rectangularity and surface roughness.

TABLE 3 Spectral variance before Visual evaluation before Example andafter solvent immersion and after solvent immersion 39 A A 40 AA AA

It can be seen from the results of Table 3, Example 40 using thedispersant C is more preferable in the viewpoints of “Spectral variancebefore and after solvent immersion” and “Visual evaluation before andafter solvent immersion” which represent solvent resistance and alkalinedeveloping solution resistance as compared to Example 39 using thedispersant A.

(Preparation of Red Pigment Dispersion)

A mixed solution composed of 8.3 parts by weight of C.I. Pigment Red 254and 3.7 parts by weight of C.I. Pigment Yellow 139 as pigments, 4.8parts by weight of BYK-161 (produced by BYK Chemie) as a pigmentdispersing agent and 83.2 parts by weight of PGMEA was mixed anddispersed in a bead mill for 15 hours to prepare Red pigment dispersionR1.

(Preparation of Blue Pigment Dispersion)

A mixed solution composed of 9.5 parts by weight of C.I. Pigment Blue15:6 and 2.4 parts by weight of C.I. Pigment Violet 23 as pigments, 5.6parts by weight of BYK-161 (produced by BYK Chemie) as a pigmentdispersing agent and 82.5 parts by weight of PGMEA was mixed anddispersed in a bead mill for 15 hours to prepare Blue pigment dispersionB1.

(Preparation of Colored Radiation-Sensitive Composition for Forming RedFilter)

Pigment dispersion: Red pigment dispersion R1 51.2 parts described abovePhotopolymerization initiator: IRGACURE OXE-01 0.87 parts (produced byBASF) Polymerizable compound: KAYARAD RP-1040 (produced 4.7 parts byNippon Kayaku Co., Ltd.) Binder: ACA230AA (produced by Daicel Corp.) 7.4parts Polymerization inhibitor: p-Methoxyphenol 0.002 parts Additive:PIONIN D-6112-W (produced by Takemoto 0.19 parts Oil & Fat Co., Ltd.)Silane coupling agent: 0.9% Cyclohexanone solution 10.8 parts of KBM-602(produced by Shin-Etsu Chemical Co., Ltd.) Organic solvent: PGMEA 14.3parts Organic solvent: Cyclohexanone 6.4 parts Fluorine-basedsurfactant: 0.2% Cyclohexanone 4.2 parts solution of F-781 (produced byDIC Corp.)

(Preparation of Colored Radiation-Sensitive Composition for Forming BlueFilter)

Pigment dispersion: Blue pigment dispersion B1 51.2 parts describedabove Photopolymerization initiator: IRGACURE OXE-01 0.87 parts(produced by BASF) Polymerizable compound: KAYARAD RP-1040 (produced 4.7parts by Nippon Kayaku Co., Ltd.) Binder: ACA230AA (produced by DaicelCorp.) 7.4 parts Polymerization inhibitor: p-Methoxyphenol 0.002 partsAdditive: PIONIN D-6112-W (produced by Takemoto 0.19 parts Oil & FatCo., Ltd.) Silane coupling agent: 0.9% Cyclohexanone solution 10.8 partsof KBM-602 (produced by Shin-Etsu Chemical Co., Ltd.) Organic solvent:PGMEA 14.3 parts Organic solvent: Cyclohexanone 6.4 parts Fluorine-basedsurfactant: 0.2% Cyclohexanone 4.2 parts solution of F-781 (produced byDIC Corp.)

Process of Forming Green Color Pattern (Green Color Pixel) by DryEtching (Formation of Green Color Layer)

The colored composition for forming green color filter for each of theexamples and comparative examples was coated on a glass wafer by a spincoater so as to form a layer having a thickness of 0.6 μm, dried by ahot plate at 100° C. for 180 seconds and then subjected to a heattreatment (post bake) using a hot plate at 200° C. for 300 seconds toform a green color layer. The thickness of the green color layer was 0.6μm.

(Coating of Resist for Mask)

Then, a positive resist (FHi622BC, produced by Fujifilm ElectronicMaterials Co., Ltd.) was coated on the green color layer and subjectedto pre bake to form a photoresist layer having a thickness of 0.8 μm.

(Pattern Exposure and Development of Resist for Mask)

Then, the photoresist layer was subjected to pattern exposure using ani-ray stepper (produced by Canon Inc.) in an exposure amount of 350mJ/cm² and then heat treatment for one minute at temperature at whichthe temperature of the photoresist layer or ambient temperature reached90° C. Then, development processing was conducted using a developer(FHD-5, produced by Fujifilm Electronic Materials Co., Ltd.) for oneminute and then a post back treatment was conducted at 110° C. for oneminute to from a resist pattern. The resist pattern formed was a patternin which square resist films each having one side length of 1.25 μm werearranged checkerwise, in consideration of an etching conversiondifference (decrease in a pattern width by etching).

(Dry Etching)

Then, using the resist pattern as an etching mask, dry etching of thegreen color layer was conducted in the procedure described below.

A first stage etching treatment was conducted for 80 seconds using a dryetching device (U-621, produced by Hitachi, Ltd.) under the conditionsof RF power: 800 W; antenna bias: 400 W; wafer bias: 200 W; innerpressure of chamber: 4.0 Pa; substrate temperature: 50 C°; and the kindand flow rate of mixed gas: CF₄: 80 ml/min, O₂: 40 ml/min and Ar: 800ml/min.

The scraping amount of the green color layer under the conditionsdescribed above was 534 nm (etching amount of 89%) and about 58 nm ofthe green color layer remained.

Then, a second stage etching treatment and an over etching treatmentwere conducted with an over-etching ratio of 20% to the total etchingusing the same etching device under the conditions of RF power: 600 W;antenna bias: 100 W; wafer bias: 250 W; inner pressure of chamber: 2.0Pa; substrate temperature: 50 C°; and the kind and flow rate of mixedgas: N₂: 500 ml/min, O₂: 50 ml/min and Ar: 500 ml/min(N₂/O₂/Ar=10/1/10).

The etching rate of the green color layer under the conditions of secondstage etching treatment was 600 nm/min or more and it took a period ofabout 10 seconds to etch the remaining green color layer. By adding 10seconds of the etching time for the second stage etching treatment to 80seconds of the etching time for the first stage etching treatment, theetching time was calculated. As a result, the etching time was 80+10=90seconds, the over-etching time was 90×0.2=18 seconds, and the totaletching time was 90+18=108 seconds.

After conducting the dry etching under conditions described above, astripping treatment was conducted using a photoresist stripping solution(MS230C, produced by Fujifilm Electronic Materials Co., Ltd.) for 120seconds to remove the resist pattern, and then washing with pure waterand spin drying were conducted. Thereafter, a dehydration bakingtreatment was conducted at 100° C. for 2 minutes. Thus, a green colorpattern in which square green color pixels each having one side lengthof 1.2 μm were arranged checkerwise was obtained.

Each green color pattern in which square green color pixels each havingone side length of 1.2 μm were arranged checkerwise and which wasprepared using the colored composition for forming green color filter ofeach of the examples in the step of forming green color pattern (greencolor pixel) by dry etching was prepared. The coloredradiation-sensitive composition for forming red filter was coated on thegreen color pattern so as that an inside of each through-hole of thegreen color pattern was filled with the colored radiation-sensitivecomposition for forming red filter and that the thickness after dryingand post bake became 0.40 μm to obtain a stacked color filter composedof the red color radiation-sensitive layer formed on the green colorlayer (corresponding to the state shown in FIG. 7).

The red color radiation-sensitive layer of the stacked color filterthus-obtained was subjected to pattern exposure using an i-ray stepper(produced by Canon Inc.) in an exposure amount of 350 mJ/cm². Theexposed areas were areas corresponding to the through-halls located ineven lines in the checkered green color pattern (corresponding to theposition 21A in the second colored radiation-sensitive layer 21corresponding to the first through-hole part group 121 formed in thefirst colored layer 11 (refer to FIG. 7)).

Then, the stacked color filter after exposure was mounted on ahorizontal rotary table of a spin shower developing machine (ModelDW-30, produced by Chemitronics Co., Ltd.) and subjected to puddledevelopment at 23° C. for 60 seconds using a 60% diluted solution ofCD-2000 (produced by Fujifilm Electronic Materials Co., Ltd.). Then, thecolor filter was fixed on the horizontal rotary table with a vacuumchuck system, and subjected to a rinse treatment by supplying a showerof pure water from a jet nozzle above the center of rotation while thecolor filter was rotated by a rotator at a rotation speed of 50 rpm,followed by spray drying.

Thus, a color filter precursor in which the red colorradiation-sensitive layer and the red color pixels formed in the insideof the through-holes located in odd lines in the checkered green colorpattern were removed was obtained (corresponding to the state shown inFIG. 8).

Then, the colored radiation-sensitive composition for forming bluefilter was coated on the color filter precursor so as that an inside ofeach through-hole of the green color pattern of the color filterprecursor was filled with the colored radiation-sensitive compositionfor forming blue filter and that the thickness after drying and postbake became 0.40 μm to obtain a stacked color filter composed of theblue color radiation-sensitive layer formed on the green color layer(corresponding to the state shown in FIG. 9).

The blue color radiation-sensitive layer of the stacked color filterthus-obtained was subjected to pattern exposure using an i-ray stepper(produced by Canon Inc.) in an exposure amount of 350 mJ/cm². Theexposed areas were areas corresponding to the through-halls located inodd lines in the checkered green color pattern (corresponding to theposition 31A in the third colored radiation-sensitive layer 31corresponding to the second through-hole part group 122 formed in thefirst colored layer 11 (refer to FIG. 9)).

Then, the stacked color filter after exposure was mounted on ahorizontal rotary table of a spin shower developing machine (ModelDW-30, produced by Chemitronics Co., Ltd.) and subjected to puddledevelopment at 23° C. for 60 seconds using a 60% diluted solution ofCD-2000 (produced by Fujifilm Electronic Materials Co., Ltd.). Then, thecolor filter was fixed on the horizontal rotary table with a vacuumchuck system, and subjected to a rinse treatment by supplying a showerof pure water from a jet nozzle above the center of rotation while thecolor filter was rotated by a rotator at a rotation speed of 50 rpm,followed by spray drying.

Thus, a color filter in which the blue color radiation-sensitive layerin the stacked color filter was removed was obtained (corresponding tothe state shown in FIG. 10).

To each of GRB color filters manufactured by combining eachgreen-colored curable composition, the colored radiation-sensitivecomposition for forming red color filter, and the coloredradiation-sensitive composition for forming blue color filter, each ofpropylene glycol monomethyl ether (PGMEA), acetone, N-methylpyrrolidone(NMP), stripping solution MS230C (manufactured by FUJIFILM ELECTRONICMATERIALS CO., LTD.), alkaline developer FHD-5 (tetramethylammoniumhydroxide (TMAH): 2.38% by mass, manufactured by FUJIFILM ELECTRONICMATERIALS CO., LTD.) was dropped and allowed them to stand for 120seconds, followed by rinsing with flowed water for 10 seconds.

The spectral variance of the transmittance before and after addingdropwise in the various liquids was measured and color difference ΔEabwas measured.

Low value of ΔEab denotes excellent solvent resistance and alkalinedeveloping solution resistance.

The green color filters of each of Examples show excellent solventresistance and alkaline developing solution resistance as compared toComparative Examples as well as the case of using the green color fiteralone.

INDUSTRIAL APPLICABILITY

Therefore, when the coloring composition is used as a first coloringcomposition in the method for preparing a color filter of the presentinvention, since the first colored layer, furthermore, the first coloredpixel is formed with a coloring composition having high concentration ofa colorant, the thickness of the first pixel can be made very thin (forexample, 0.7 μm or less). Accordingly, a color filter in which crosstalk(color mixing of light) is suppressed can be manufactured with themethod.

Further, the first pixel formed with the coloring composition of thepresent invention has excellent solvent resistance and alkalinedeveloping solution resistance. Accordingly, the occurrence of overlapregion overlapped with colors in other colored layers and other coloredpatterns may be reduced, and as a result, a high performance colorfilter may be prepared.

This application is based on a Japanese patent application filed on Aug.31, 2011 (Japanese Patent Application No. 2011-190186), and the contentsthereof are incorporated herein by reference.

1. A coloring composition comprising: a colorant; and a resin, wherein acontent of the colorant is 50% by mass or more based on total solids ofthe coloring composition, and a solid acid number of a resin having ahighest solid acid number among all kinds of resins contained in thecoloring composition, is 80 mg KOH/g or less.
 2. A method formanufacturing a color filter comprising: (a) forming a first coloredlayer including a first coloring composition; and (b) patterning thefirst coloring composition by dry etching to form a group ofthrough-holes in the first colored layer, wherein the first coloringcomposition is the coloring composition according to claim
 1. 3. Themethod according to claim 2, wherein the group of through-holes includesa first group of through-holes and a second group of through-holes, themethod further comprising: (c) stacking a second colored radiationsensitive layer including a second coloring radiation sensitivecomposition on the first colored layer so that the second coloringradiation sensitive composition is embedded inside each of thethrough-holes in the first group of the through-holes and the secondgroup of the through-holes so as to form a plurality of second coloredpixels; (d) removing the second colored radiation sensitive layer and aplurality of the second colored pixels formed inside each of thethrough-holes in the second group of the through-holes by exposing anddeveloping a position in the second colored radiation sensitive layer,which corresponds to the first group of the through-holes formed in thefirst colored layer; (e) stacking a third colored radiation sensitivelayer including a third coloring radiation sensitive composition on thefirst colored layer so that the third coloring radiation sensitivecomposition is embedded inside each of the through-holes in the secondgroup of the through-holes so as to form a plurality of third coloredpixels; and (f) removing the third colored radiation sensitive layer byexposing and developing a position in the third colored radiationsensitive layer, which corresponds to the second group of thethrough-holes formed in the first colored layer.
 4. The method accordingto claim 3, wherein the second coloring radiation sensitive compositioncontains a colorant in amount of 30% by mass or more based on totalsolids of the second coloring radiation sensitive composition, and thethird coloring radiation sensitive composition contains a colorant inamount of 30% by mass or more based on total solids of the thirdcoloring radiation sensitive composition, and the second coloringcomposition contains a colorant in amount of 30% by mass or more basedon total solids of the third coloring radiation sensitive composition.5. The method according to claim 2, wherein the first colored layer is agreen transmitting layer.
 6. The method according to claim 5, whereinone of the second pixels and the third pixels is a red transmittingpart, and the other is blue transmitting part.
 7. A color filterobtained by the method for preparing a color filter according to claim2.
 8. A solid-state imaging device comprising the color filter of claim7.